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Sample records for absolute isotopic composition

  1. Uranium isotopic composition and absolute ages of Allende chondrules

    NASA Astrophysics Data System (ADS)

    Brennecka, G. A.; Budde, G.; Kleine, T.

    2015-11-01

    A handful of events, such as the condensation of refractory inclusions and the formation of chondrules, represent important stages in the formation and evolution of the early solar system and thus are critical to understanding its development. Compared to the refractory inclusions, chondrules appear to have a protracted period of formation that spans millions of years. As such, understanding chondrule formation requires a catalog of reliable ages, free from as many assumptions as possible. The Pb-Pb chronometer has this potential; however, because common individual chondrules have extremely low uranium contents, obtaining U-corrected Pb-Pb ages of individual chondrules is unrealistic in the vast majority of cases at this time. Thus, in order to obtain the most accurate 238U/235U ratio possible for chondrules, we separated and pooled thousands of individual chondrules from the Allende meteorite. In this work, we demonstrate that no discernible differences exist in the 238U/235U compositions between chondrule groups when separated by size and magnetic susceptibility, suggesting that no systematic U-isotope variation exists between groups of chondrules. Consequently, chondrules are likely to have a common 238U/235U ratio for any given meteorite. A weighted average of the six groups of chondrule separates from Allende results in a 238U/235U ratio of 137.786 ± 0.004 (±0.016 including propagated uncertainty on the U standard [Richter et al. 2010]). Although it is still possible that individual chondrules have significant U isotope variation within a given meteorite, this value represents our best estimate of the 238U/235U ratio for Allende chondrules and should be used for absolute dating of these objects, unless such chondrules can be measured individually.

  2. Determination of the absolute isotopic composition and Atomic Weight of a reference sample of natural iron

    NASA Astrophysics Data System (ADS)

    Taylor, P. D. P.; Maeck, R.; de Bièvre, P.

    1992-11-01

    Absolute values have been obtained by means of thermal ionisation mass spectrometry for the iron isotope abundance ratios of a sample of metallic iron of natural isotopic composition. This was achieved by calibrating the mass spectrometric measurement procedure using five different synthetic isotope mixtures, prepared from carefully characterised enriched isotope carrier compounds, viz. 54Fe2O3 and 56Fe2O3. These mixtures were made up at three different n(54Fe)/n(56Fe) ratios, covering a ratio range of more than two orders of magnitude, in order to determine the extent of the isotope fractionation in the ion source. Two mixtures bracket the natural ratio, two mixtures have ratio values approximating to unity, and one mixture has a ratio of about 10. The total relative uncertainty on the ratio values of the mixtures varies between 2 and 7 × 10-4 (2s). Three different mass spectrometric measurement procedures were developed, all using a silica-gel/boric acid ionisation enhancer. Measurements were carried out on two different instruments. The n(54Fe)/n(56Fe) ratio of the synthetic mixtures and of the natural iron isotopic reference material (IRM) were measured using a mass spectrometer with Faraday detector. Both the n(57Fe)/n(56Fe) and n(58Fe)/n(56Fe) ratios of the natural iron IRM were determined using the same instrument but operated at a higher ionisation temperature (1430°C instead of 1350°C) and using an internal normalisation procedure. For the determination of the abundances of the minor isotopes in the enriched isotope carrier compounds, an instrument equipped with a calibrated ion counting device was used and the ionisation temperature was 1150°C. Using the latter instrument and method, the n(54Fe)/n(56Fe) ratio of the IRM was found to a gree within 4 × 10-5 with the calibrated value of the Faraday measurements, indicating that experimental conditions were well controlled in both cases. Compared to the current IUPAC data (Atomic Weights of the Elements

  3. Absolute isotopic abundances of TI in meteorites

    NASA Astrophysics Data System (ADS)

    Niederer, F. R.; Papanastassiou, D. A.; Wasserburg, G. J.

    1985-03-01

    The absolute isotope abundance of Ti has been determined in Ca-Al-rich inclusions from the Allende and Leoville meteorites and in samples of whole meteorites. The absolute Ti isotope abundances differ by a significant mass dependent isotope fractionation transformation from the previously reported abundances, which were normalized for fractionation using 46Ti/48Ti. Therefore, the absolute compositions define distinct nucleosynthetic components from those previously identified or reflect the existence of significant mass dependent isotope fractionation in nature. The authors provide a general formalism for determining the possible isotope compositions of the exotic Ti from the measured composition, for different values of isotope fractionation in nature and for different mixing ratios of the exotic and normal components.

  4. Absolute isotopic composition of molybdenum and the solar abundances of the p-process nuclides Mo92,94

    NASA Astrophysics Data System (ADS)

    Wieser, M. E.; de Laeter, J. R.

    2007-05-01

    The isotopic composition of molybdenum has been measured with high precision using a thermal ionization mass spectrometer, the linearity of which has been verified by measuring the isotopically-certified reference material for strontium (NIST 987). The abundance sensitivity of the mass spectrometer in the vicinity of the molybdenum ion beams has been carefully examined to ensure the absence of tailing effects. Particular care was given to ensuring that potential isobaric interferences from zirconium and ruthenium did not affect the measurement of the isotopic composition of molybdenum. Gravimetric mixtures of two isotopically enriched isotopes, Mo92 and Mo98, were analyzed mass spectrometrically to calibrate the mass spectrometer, in order to establish the isotope fractionation of the spectrometer for the molybdenum isotopes. This enabled the “absolute” isotopic composition of molybdenum to be determined. An accurate determination of the isotopic composition is required in order to calculate the atomic weight of molybdenum, which is one of the least accurately known values of all the elements. The absolute isotope abundances (in atom %) of molybdenum measured in this experiment are as follows: Mo92=14.5246±0.0015; Mo94=9.1514±0.0074; Mo95=15.8375±0.0098; Mo96=16.672±0.019; Mo97=9.5991±0.0073; Mo98=24.391±0.018; and Mo100=9.824±0.050, with uncertainties at the 1s level. These values enable an atomic weight Ar(Mo) of 95.9602±0.0023 (1s) to be calculated, which is slightly higher than the current Standard Atomic Weight Ar(Mo) =95.94±0.02 and with a much improved uncertainty interval. These “absolute” isotope abundances also enable the Solar System abundances of molybdenum to be calculated for astrophysical purposes. Of particular interest are the Solar System abundances of the two p-process nuclides—Mo92 and Mo94, which are present in far greater abundance than p-process theory suggests. The Solar System abundances for Mo92 and Mo94 of 0.364±0

  5. Insights from fossil coral U-Th age data from the Last Interglacial: Implications for seawater U-isotope composition and interpretation of absolute ages

    NASA Astrophysics Data System (ADS)

    Dutton, A.; Esat, T. M.

    2011-12-01

    significantly higher than that of modern seawater at sites around the globe, raising the possibility that seawater compositions during the Last Interglacial were also correspondingly higher. Unfortunately, without the traditional U-isotope diagenetic screening criterion it remains difficult to separate out 'altered' corals versus 'unaltered' corals; hence interpretation of the distribution of initial [234U/238U] in this Last Interglacial database requires assumptions about the effects of open-system diagenesis on this distribution. The adopted seawater [234U/238U] value for screening closed-system ages or for calculating ages using an open-system model will ultimately have an effect on the interpretation of the absolute age of the coral(s) in question. Adopting a higher seawater [234U/238U] value than modern seawater will result in an older interpreted age than for the scenario where the modern seawater value is adopted. This observation highlights the need to better characterize past uranium isotope variability in the oceans as we seek to provide increasingly stringent chronological constraints on past sea level change.

  6. Absolute photoneutron cross sections of Sm isotopes

    SciTech Connect

    Gheorghe, I.; Glodariu, T.; Utsunomiya, H.; Filipescu, D.; Nyhus, H.-T.; Renstrom, T.; Tesileanu, O.; Shima, T.; Takahisa, K.; Miyamoto, S.

    2015-02-24

    Photoneutron cross sections for seven samarium isotopes, {sup 144}Sm, {sup 147}Sm, {sup 148}Sm, {sup 149}Sm, {sup 150}Sm, {sup 152}Sm and {sup 154}Sm, have been investigated near neutron emission threshold using quasimonochromatic laser-Compton scattering γ-rays produced at the synchrotron radiation facility NewSUBARU. The results are important for nuclear astrophysics calculations and also for probing γ-ray strength functions in the vicinity of neutron threshold. Here we describe the neutron detection system and we discuss the related data analysis and the necessary method improvements for adapting the current experimental method to the working parameters of the future Gamma Beam System of Extreme Light Infrastructure - Nuclear Physics facility.

  7. Measurement of Absolute Carbon Isotope Ratios: Mechanisms and Implications

    NASA Astrophysics Data System (ADS)

    Vogel, J. S.; Giacomo, J. A.; Dueker, S. R.

    2012-12-01

    An accelerator mass spectrometer (AMS) produced absolute isotope ratio measurements for 14C/13C as tested against >500 samples of NIST SRM-4990-C (OxII 14C standard) to an accuracy of 2.2±0.6‰ over a period of one year with measurements made to 1% counting statistics. The spectrometer is not maximized for 13C/12C, but measured ∂13C to 0.4±0.1‰ accuracy, with known methods for improvement. An AMS produces elemental anions from a sputter ion source and includes a charge-changing collision in a gas cell to isolate the rare 14C from the common isotopes and molecular isobars. Both these physical processes have been modeled to determine the parameters providing such absolute measures. Neutral resonant ionization in a cesium plasma produces mass-independent ionization, while velocity dependent charge-state distributions in gas collisions produce relative ion beam intensities that are linear in mass at specific collision energies. The mechanisms are not specific to carbon isotopes, but stand alone absolute IRMS (AIR-MS) instruments have not yet been made. Aside from the obvious applications in metrology, AIR-MS is particularly valuable in coupled separatory MS because no internal or external standards are required. Sample definition processes can be compared, even if no exact standard reference sample exists. Isotope dilution measurements do not require standards matching the dilution end-points and can be made over an extended, even extrapolated, range.

  8. Atomic Weights and Isotopic Compositions

    National Institute of Standards and Technology Data Gateway

    SRD 144 Atomic Weights and Isotopic Compositions (Web, free access)   The atomic weights are available for elements 1 through 111, and isotopic compositions or abundances are given when appropriate.

  9. Magnesium isotopic composition of achondrites

    NASA Astrophysics Data System (ADS)

    Sedaghatpour, Fatemeh; Teng, Fang-Zhen

    2016-02-01

    Magnesium isotopic compositions of 22 well-characterized differentiated meteorites including 7 types of achondrites and pallasite meteorites were measured to estimate the average Mg isotopic composition of their parent bodies and evaluate Mg isotopic heterogeneity of the solar system. The δ26Mg values are -0.236‰ and -0.190‰ for acapulcoite-lodranite and angrite meteorites, respectively and vary from -0.267‰ to -0.222‰ in the winonaite-IAB-iron silicate group, -0.369‰ to -0.292‰ in aubrites, -0.269‰ to -0.158‰ in HEDs, -0.299‰ to -0.209‰ in ureilites, -0.307‰ to -0.237‰ in mesosiderites, and -0.303‰ to -0.238‰ in pallasites. Magnesium isotopic compositions of most achondrites and pallasite meteorites analyzed here are similar and reveal no significant isotopic fractionation. However, Mg isotopic compositions of D‧Orbigny (angrite) and some HEDs are slightly heavier than chondrites and the other achondrites studied here. The slightly heavier Mg isotopic compositions of angrites and some HEDs most likely resulted from either impact-induced evaporation or higher abundance of clinopyroxene with the Mg isotopic composition slightly heavier than olivine and orthopyroxene. The average Mg isotopic composition of achondrites (δ26Mg = -0.246 ± 0.082‰, 2SD, n = 22) estimated here is indistinguishable from those of the Earth (δ26Mg = -0.25 ± 0.07‰; 2SD, n = 139), chondrites (δ26Mg = -0.28 ± 0.06‰; 2SD, n = 38), and the Moon (δ26Mg = -0.26 ± 0.16‰; 2SD, n = 47) reported from the same laboratory. The chondritic Mg isotopic composition of achondrites, the Moon, and the Earth further reflects homogeneity of Mg isotopes in the solar system and the lack of Mg isotope fractionation during the planetary accretion process and impact events.

  10. Grosnaja ABCs: Magnesium isotope compositions

    NASA Technical Reports Server (NTRS)

    Goswami, J. N.; Srinivasan, G.; Ulyanov, A. A.

    1993-01-01

    Three CAI's from the Grosnaja CV3 chondrite were analyzed for their magnesium isotopic compositions by the ion microprobe. The selected CAI's represent three distinct types: GR4(compact Type A), GR7(Type B) and GR2(Type C). Petrographic studies indicate that all three Grosnaja inclusions were subjected to secondary alterations. The Type A CAI GR4 is primarily composed of melilite with spinel and pyroxene occurring as minor phases. The rim of the inclusion does not exhibit distinct layered structure and secondary alteration products (garnet, Fe-rich olivine and Na-rich plagioclase) are present in some localized areas near the rim region. The average major element compositions of different mineral phases in GR4 are given. Preliminary REE data suggest a depletion of HREE relative to LREE by about a factor of 3 without any clear indication of interelement fractionation. The CAI GR7 has textural and minerological characteristics similar to Type B inclusions. The REE data show a pattern that is similar to Group 6 with enrichment in Eu and Yb. In addition, a depletion of HREE compared to LREE is also evident in this object. Melilite composition shows a broad range of akermanite content (Ak(sub 15-55)). Detailed petrographic study is in progress. GR2 is a anorthite-rich Type C inclusion with large plagioclase laths intergrown with Ti-rich pyroxene. The average plagioclase composition is close to pure anorthite (An99).

  11. Metal Stable Isotope Tagging: Renaissance of Radioimmunoassay for Multiplex and Absolute Quantification of Biomolecules.

    PubMed

    Liu, Rui; Zhang, Shixi; Wei, Chao; Xing, Zhi; Zhang, Sichun; Zhang, Xinrong

    2016-05-17

    The unambiguous quantification of biomolecules is of great significance in fundamental biological research as well as practical clinical diagnosis. Due to the lack of a detectable moiety, the direct and highly sensitive quantification of biomolecules is often a "mission impossible". Consequently, tagging strategies to introduce detectable moieties for labeling target biomolecules were invented, which had a long and significant impact on studies of biomolecules in the past decades. For instance, immunoassays have been developed with radioisotope tagging by Yalow and Berson in the late 1950s. The later languishment of this technology can be almost exclusively ascribed to the use of radioactive isotopes, which led to the development of nonradioactive tagging strategy-based assays such as enzyme-linked immunosorbent assay, fluorescent immunoassay, and chemiluminescent and electrochemiluminescent immunoassay. Despite great success, these strategies suffered from drawbacks such as limited spectral window capacity for multiplex detection and inability to provide absolute quantification of biomolecules. After recalling the sequences of tagging strategies, an apparent question is why not use stable isotopes from the start? A reasonable explanation is the lack of reliable means for accurate and precise quantification of stable isotopes at that time. The situation has changed greatly at present, since several atomic mass spectrometric measures for metal stable isotopes have been developed. Among the newly developed techniques, inductively coupled plasma mass spectrometry is an ideal technique to determine metal stable isotope-tagged biomolecules, for its high sensitivity, wide dynamic linear range, and more importantly multiplex and absolute quantification ability. Since the first published report by our group, metal stable isotope tagging has become a revolutionary technique and gained great success in biomolecule quantification. An exciting research highlight in this area

  12. Isotopic composition of gases from mud volcanoes

    SciTech Connect

    Valysaev, B.M.; Erokhin, V.E.; Grinchenko, Y.I.; Prokhorov, V.S.; Titkov, G.A.

    1985-09-01

    A study has been made of the isotopic composition of the carbon in methane and carbon dioxide, as well as hydrogen in the methane, in the gases of mud volcanoes, for all main mud volcano areas in the USSR. The isotopic composition of carbon and hydrogen in methane shows that the gases resemble those of oil and gas deposits, while carbon dioxide of these volcanoes has a heavier isotopic composition with a greater presence of ''ultraheavy'' carbon dioxide. By the chemical and isotopic composition of gases, Azerbaidzhan and South Sakhalin types of mud volcano gases have been identified, as well as Bulganak subtypes and Akhtala and Kobystan varieties. Correlations are seen between the isotopic composition of gases and the geological build of mud volcano areas.

  13. Isotopic compositions of the elements, 2001

    USGS Publications Warehouse

    Böhlke, J.K.; De Laeter, J. R.; De Bievre, P.; Hidaka, H.; Peiser, H.S.; Rosman, K.J.R.; Taylor, P.D.P.

    2005-01-01

    The Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry completed its last review of the isotopic compositions of the elements as determined by isotope-ratio mass spectrometry in 2001. That review involved a critical evaluation of the published literature, element by element, and forms the basis of the table of the isotopic compositions of the elements (TICE) presented here. For each element, TICE includes evaluated data from the "best measurement" of the isotope abundances in a single sample, along with a set of representative isotope abundances and uncertainties that accommodate known variations in normal terrestrial materials. The representative isotope abundances and uncertainties generally are consistent with the standard atomic weight of the element A r(E) and its uncertainty U[Ar(E)] recommended by CAWIA in 2001. ?? 2005 American Institute of Physics.

  14. Magnesium isotopic composition of the mantle

    NASA Astrophysics Data System (ADS)

    Teng, F.; Li, W.; Ke, S.; Marty, B.; Huang, S.; Dauphas, N.; Wu, F.; Helz, R. L.

    2009-12-01

    Studies of Mg isotopic composition of the Earth not only are important for understanding its geochemistry but also can shed light on the accretion history of the Earth as well as the evolution of the Earth-Moon system. However, to date, the Mg isotopic composition of the Earth is still poorly constrained and highly debated. There is uncertainty in the magnitude of Mg isotope fractionation at mantle temperatures and whether the Earth has a chondritic Mg isotopic composition or not. To constrain further the Mg isotopic composition of the mantle and investigate the behavior of Mg isotopes during igneous differentiation, we report >200 high-precision (δ26Mg < 0.1‰, 2SD) analyses of Mg isotopes on 1) global mid-ocean ridge basalts covering major ridge segments of the world and spanning a broad range in latitudes, chemical and radiogenic isotopic compositions; 2) ocean island basalts from Hawaiian (Koolau, Kilauea and Loihi) and French Polynesian volcanoes (Society island and Cook Austral chain); 3) olivine grains from Hawaiian volcanoes (Kilauea, Koolau and Loihi) and 4) peridotite xenoliths from Australia, China, France, Tanzania and USA. Global oceanic basalts and peridotite xenoliths have a limited (<0.2 ‰) variation in Mg isotopic composition, with an average δ26Mg = -0.25 relative to DSM3. Olivines from Hawaiian lavas have δ26Mg ranging from -0.43 to +0.03, with most having compositions identical to basalts and peridotites. Therefore, the mantle’s δ26Mg value is estimated to be ~ -0.25 ± 0.1 (2SD), different from that reported by Wiechert and Halliday (2007; δ26Mg = ~ 0) but similar to more recent studies (δ26Mg = -0.27 to -0.33) (Teng et al. 2007; Handler et al. 2009; Yang et al., 2009). Moreover, we suggest the Earth, as represented by the mantle, has a Mg isotopic composition similar to chondrites (δ26Mg = ~-0.33). The need for a model such as that of Wiechert and Halliday (2007) that involves sorting of chondrules and calcium

  15. Isotopic Compositions of Evaporative Fluxes

    NASA Astrophysics Data System (ADS)

    Feng, X.; Lauder, A. M.; Kopec, B. G.; Dade, W. B.; Virginia, R. A.; Posmentier, E. S.

    2013-12-01

    The isotopic fluxes of evaporation from a water surface are typically computed using a one-dimensional model, originally conceptualized by Craig and Gordon (1965) and further developed and adapted to different natural settings (such as transpiration, open surface evaporation, etc.) by various investigators. These models have two distinguishing characteristics. First, there exists a laminar layer where molecular diffusion away from the water-air interface causes kinetic isotopic fractionation. The magnitude of this fractionation is controlled by the diffusion/transport coefficient of each vapor isotopologue in air and their concentration gradients, the latter being controlled by relative humidity, isotopic ratios of ambient air, and turbulent conditions (such as wind and surface roughness). Second, the horizontal variations are ignored. In particular, the effect of horizontal advection on isotopic variations in the ambient air is not considered. The research reported here addresses the effects of relinquishing the simplifying assumptions in both of these areas. We developed a model, in which the simplification of a purely laminar layer is dropped. Instead, we express the vertical transport coefficient as the sum of the molecular diffusivity, that differs for each water isotopologue, and the turbulent diffusivity that increases linearly with height but does not vary among water isotopologues. With this model, the kinetic isotopic effect reduces with height in the vicinity of the water surface, and the net isotopic fractionation through the boundary layer can be integrated. The advantage of this conceptualization is that the magnitude of kinetic isotopic fractionation can be assessed directly with changing environmental conditions, such as humidity and wind speed, rather than approximated by discontinuous empirical functions of the environmental conditions, as in the conventional models mentioned above. To address the effect of lateral heterogeneity, we expanded the

  16. Unusual mercury isotopic compositions in aqueous environment

    NASA Astrophysics Data System (ADS)

    Chen, J.; Hintelmann, H.; Zheng, W.; Feng, X.; Cai, H.; Wang, Z.; Yuan, S.

    2014-12-01

    Preliminary studies have demonstrated both mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) of Hg isotopes in natural samples. Laboratory experiments showed that photochemical reduction of inorganic mercury (iHg) and methylmercury (MMHg) and liquid-vapour evaporation could produce MIF of odd Hg isotopes. This was thought to cause the MIF actually observed in aquatic organisms. Although isotopic measurements of Hg in aqueous environment would give direct evidence, little data was reported for surface water samples. Recent work reported, unexpectedly, positive MIF of odd Hg isotopes in both precipitation and ambient air, in contrast with the prediction of laboratory experiments and measurements of Hg accumulated in lichens . Intriguingly, MIF of even-mass Hg isotope (200Hg) was also recently determined in the atmosphere. In contrast with the now mainstream observation of odd Hg isotope anomaly that has several theoretical explanations, the hitherto mysterious even Hg isotope anomalies were neither reported in laboratory experiments, nor predicted by isotope fractionation mechanisms, highlighting the importance of further study on Hg isotopes in variable systems. Our measurements of lichens and lake water samples from different countries show for the first time significant Δ200Hg in surface terrestrial reservoirs, realizing a direct connection of even Hg isotope anomaly in the terrestrial reservoirs to the atmospheric deposition, and fulfilling the gap of Δ200Hg between the atmosphere and the terrestrial receptors. The specific odd Hg isotope compositions determined in lake waters also support the atmosphere contribution, and may be directly linked to the high Δ199Hg values largely determined and manifested on the top of aqueous food web. Our data show that the watershed Hg input is another contributing source, rather than the in-lake processes, to explain the lacustrine Hg isotope anomalies. Interestingly, lake sediments are isotopically

  17. Carbon isotopic composition of Amazon shelf sediments

    SciTech Connect

    Showers, W.J.; Angle, D.G.; Nittrouer, C.A.; Demaster, D.J.

    1985-02-01

    The distribution of carbon isotopes in Amazon shelf sediment is controlled by the same processes that are forming the modern subaqueous delta. The terrestrial (-27 to -25 per thousand) isotopic carbon signal observed in surficial sediments near the river mouth extends over 400 km northwest along the shelf. Terrestrial carbon is associated with areas of rapid sediment accumulation (topset and foreset regions). A sharp boundary between terrestrial (-27 to -25 per thousand) and marine (-23 to -22 per thousand) isotopic carbon values in surficial sediments is associated with a change in depositional conditions (foreset to bottomset regions) and a decrease in sediment accumulation rate. POC water-column isotopic values (-27 per thousand) near the river mouth are similar to the underlying surficial-sediment TOC isotopic values, but POC water-column samples collected 20 km off the river mouth have marine carbon isotopic values (-22 to -19 per thousand) and differ from the underlying surficial-sediment TOC isotopic values. These water column observations are related to variations in turbidity and productivity. Down-core isotopic variation is only observed in cores taken in areas of lower sediment accumulation rates. These observations indicate that the organic carbon in Amazon shelf sediment is dominantly terrestrial in composition, and the location of deposition of this carbon is controlled by modern processes of sediment accumulation. The modern Amazon shelf is similar to large clinoform shale deposits of the Cretaceous in North America. Thus, the stratigraphic setting may help predict the isotopic variations of carbon in ancient deposits.

  18. Nucleosynthesis and the Isotopic Composition of Stardust

    NASA Technical Reports Server (NTRS)

    Tielens, Alexander G. M.

    1997-01-01

    Various components have been isolated from carbonaceous meteorites with an isotopically anomalous elemental composition. Several of these are generally thought to represent stardust containing a nucleosynthetic record of their birthsites. This paper discusses the expected isotopic composition of stardust based upon astronomical observations and theoretical studies of their birthsites: red giants and supergiants, planetary nebulae, C-rich Wolf-Rayet stars, novae and supernovae. Analyzing the stardust budget, it is concluded that about 15% of the elements will be locked up in stardust components in the interstellar medium. This stardust will be isotopically heterogenous on an individual grain basis by factors ranging from 2 to several orders of magnitude. Since comets may have preserved a relatively unprocessed record of the stardust entering the solar nebula, isotopic studies of returned comet samples may provide valuable information on the nucleosynthetic processes taking place in the interiors of stars and the elemental evolution of the Milky Way.

  19. Stable isotope composition of Earth's large lakes

    NASA Astrophysics Data System (ADS)

    Jasechko, S.; Gibson, J. J.; YI, Y.; Birks, S. J.; Sharp, Z. D.

    2011-12-01

    Lakes cover about three percent of Earth's continental area. Large lakes can significantly influence lake shore and regional climates by increasing specific humidity during evaporation and by moderating air temperatures. Stable isotopes of oxygen and hydrogen can be used to quantify lake evaporation, providing a supplementary and often cost-advantageous alternative to conventional hydrologic approaches that require over lake monitoring. Further, stable isotopes in lake sediments are an established tool in paleolimnology; however, interpreting changes to a lake's past isotope composition requires a comprehensive understanding of contemporary controls. Here, δ18O and δ2H values of water in modern lakes exceeding roughly five hundred square kilometres are compiled (n > 35). Voluminous and seasonally mixed lakes - such as the North American Great Lakes - have the most homogenous stable isotope compositions, while perennially-stratified and shallow lakes show greater variability. A rudimentary stable isotope mass balance is used to assess evaporation fluxes from large lakes on Earth. The approach taken simultaneously constrains evaporation outputs for both oxygen and hydrogen stable isotopes by accounting for lake effects on the overlying atmosphere. Model development highlights important considerations such as isotopic stratification (Tanganyika), disequilibrium isotopic mass balances (Baikal), and non-steady hydrologic balances. Further, the isotope composition of Earth's continental surface water reservoir is calculated. This value - weighted to volume - is δ18O = -7.5±1.7 per mille relative to standard mean ocean water. The compiled data may be a useful tracer of continental evaporate in global atmospheric water cycle studies and could be coupled to climate models capable of incorporating oxygen-18 and deuterium tracers to improve or validate calculations of lake effects on regional water cycling.

  20. Recombinant isotope labeled and selenium quantified proteins for absolute protein quantification.

    PubMed

    Zinn, Nico; Winter, Dominic; Lehmann, Wolf D

    2010-03-15

    A novel, widely applicable method for the production of absolutely quantified proteins is described, which can be used as internal standards for quantitative proteomic studies based on mass spectrometry. These standards are recombinant proteins containing an isotope label and selenomethionine. For recombinant protein expression, assembly of expression vectors fitted to cell-free protein synthesis was conducted using the gateway technology which offers fast access to a variety of genes via open reading frame libraries and an easy shuttling of genes between vectors. The proteins are generated by cell-free expression in a medium in which methionine is exchanged against selenomethionine and at least one amino acid is exchanged by a highly stable isotope labeled analogue. After protein synthesis and purification, selenium is used for absolute quantification by element mass spectrometry, while the heavy amino acids in the protein serve as reference in subsequent analyses by LC-ESI-MS or MALDI-MS. Accordingly, these standards are denominated RISQ (for recombinant isotope labeled and selenium quantified) proteins. In this study, a protein was generated containing Lys+6 ([(13)C(6)]-lysine) and Arg+10 ([(13)C(6),(15)N(4)]-arginine) so that each standard tryptic peptide contains a labeled amino acid. Apolipoprotein A1 was synthesized as RISQ protein, and its use as internal standard led to quantification of a reference material within the specified value. Owing to their cell-free expression, RISQ proteins do not contain posttranslational modifications. Thus, correct quantitative data by ESI- or MALDI-MS are restricted to quantifications based on peptides derived from unmodified regions of the analyte protein. Therefore, besides serving as internal standards, RISQ proteins stand out as new tools for quantitative analysis of covalent protein modifications. PMID:20163147

  1. Isotopic Compositions of Uranium Reference Materials

    NASA Astrophysics Data System (ADS)

    Jacobsen, B.; Borg, L. E.; Williams, R. W.; Brennecka, G.; Hutcheon, I. D.

    2009-12-01

    Uranium isotopic compositions of a variety of U standard materials were measured at Lawrence Livermore National Laboratory and are reported here. Both thermal ionization mass spectrometry (TIMS) and multi-collector inductively couple plasma mass spectrometry (MC-ICPMS) were used to determine ratios of the naturally occurring isotopes of U. Establishing an internally coherent set of isotopic values for a range of U standards is essential for inter-laboratory comparison of small differences in 238U/235U, as well as the minor isotopes of U. Differences of ~1.3‰ are now being observed in 238U/235U in natural samples, and may play an important role in understanding U geochemistry where tracing the origin of U is aided by U isotopic compositions. The 238U/235U ratios were measured with a TRITON TIMS using a mixed 233U-236U isotopic tracer to correct for instrument fractionation. This tracer was extremely pure and resulted in only very minor corrections on the measured 238U/235U ratios of ~0.03. The values obtained for 238U/235U are: IRMM184 = 137.698 ± 0.020 (n=15), SRM950a = 137.870 ± 0.018 (n=8), and CRM112a = 137.866 ± 0.030 (n=16). Uncertainties represent 2 s.d. of the population. Our measured value for IRMM184 is in near-perfect agreement with the certified value of 137.697 ± 0.042. However, the U isotopic compositions of SRM950a and CRM112a are not certified. Minor isotopes of U were determined with a Nu Plasma HR MC-ICPMS and mass bias was corrected by sample/standard bracketing to IRMM184, using its certified 238U/235U ratio. Thus, the isotopic compositions determined using both instruments are compatible. The values obtained for 234U/235U are: SRM950a = (7.437 ± 0.043)x10-3 (n=18), and CRM112a = (7.281 ± 0.050)x10-3 (n=16), both of which are in good agreement with published values. The value for 236U/235U in SRM950a was determined to be (8.48 ± 2.63)x10-6, whereas 236U was not detected in CRM112a. We are currently obtaining the U isotopic composition of

  2. Carbon isotope composition of Antarctic plants

    NASA Astrophysics Data System (ADS)

    Galimov, E. M.

    2000-05-01

    Carbon isotope compositions of Antarctic land plants are first reported. The most interesting feature is the isotope specificity of the species. For example Usnea antarctica from different locations shows relatively narrow range of the δ 13C-values from -22.44 to -21.29‰ (7 samples), Drepanocladus sp. from -24.86 to -23.49‰ (8 samples), and Andreaea depressincrvis from -23.87 to -23.23‰ (3 samples) etc. Usually, in inhabited lands and parts of the world with rich flora and developed soil, isotopic specificity of species is masked by variations of carbon isotope composition of CO 2. In Antarctic conditions influence of local sources of CO 2 on the isotope composition of CO 2 is appeared to be minimal. Therefore the δ 13C-variations inherent to individual plant physiology and biochemistry can be distinguished on the background of the stable level of the atmospheric CO 2 δ 13C-value. The latter is best to reflect the global state of the carbon cycle.

  3. Hydrogen isotope composition of magmatic water

    SciTech Connect

    Taylor, B.E. )

    1992-01-01

    Isotopic tracing of H[sub 2]O degassing in both small and very large rhyolitic magmas in continental tectonic settings (USA and New Zealand), and isotopic studies of high-temperature fumaroles (USA, Japan, and elsewhere) indicate that the hydrogen isotope compositions of magmatic waters vary primarily with the composition of source material and tectonic setting. Water from felsic magmas in volcanic arc settings has a mean [delta]D value off [minus]25 [+-] 5 permil, whereas water from volcanic and plutonic magmas in continental settings has a slightly lower mean [delta]D of [minus]40 [+-] 10 permil. These differences reflect the variation in composition of source materials: hydrated oceanic crust and marine sediments for the arc volcanoes, and largely metamorphic crust for magmas in continental settings. The isotopic record in certain ore deposits associated with felsic magmas (e.g., W skarns, Sn-W veins) and geothermal systems records the influx at critical times of magmatic water with a [delta]D value of [minus]35 to [minus]45 permil. This is best documented where isotopic contrast between magmatic and meteoric waters is large. The [delta]D of MORB H[sub 2]O presumably lies between the mean [delta]D for MORB glass ([minus]75 permil), the [delta]D of H[sub 2]O in equilibrium with this glass ([delta]D ca. [minus]35; assuming closed-system degassing).

  4. Calcium isotopic composition of mantle peridotites

    NASA Astrophysics Data System (ADS)

    Huang, F.; Kang, J.; Zhang, Z.

    2015-12-01

    Ca isotopes are useful to decipher mantle evolution and the genetic relationship between the Earth and chondrites. It has been observed that Ca isotopes can be fractionated at high temperature [1-2]. However, Ca isotopic composition of the mantle peridotites and fractionation mechanism are still poorly constrained. Here, we report Ca isotope composition of 12 co-existing pyroxene pairs in 10 lherzolites, 1 harzburgite, and 1 wehrlite xenoliths collected from Hainan Island (South Eastern China). Ca isotope data were measured on a Triton-TIMS using the double spike method at the Guangzhou Institute of Geochemistry, CAS. The long-term external error is 0.12‰ (2SD) based on repeated analyses of NIST SRM 915a and geostandards. δ44Ca of clinopyroxenes except that from the wehrlite ranges from 0.85‰ to 1.14‰, while opx yields a wide range from 0.98‰ up to 2.16‰. Co-existing pyroxene pairs show large ∆44Caopx-cpx (defined as δ44Caopx-δ44Cacpx) ranging from 0 to 1.23‰, reflecting equilibrium fractionation controlled by variable Ca contents in the opx. Notably, clinopyroxene of wehrlite shows extremely high δ44Ca (3.22‰). δ44Ca of the bulk lherzolites and harzburgites range from 0.86‰ to 1.14‰. This can be explained by extracting melts with slightly light Ca isotopic compositions. Finally, the high δ44Ca of the wehrlite (3.22‰) may reflect metasomatism by melt which has preferentially lost light Ca isotopes due to chemical diffusion during upwelling through the melt channel. [1] Amini et al (2009) GGR 33; [2] Huang et al (2010) EPSL 292.

  5. The Chlorine Isotope Composition of Martian Meteorites

    NASA Astrophysics Data System (ADS)

    Sharp, Z. D.; Shearer, C. K.; Agee, C.; Burger, P. V.; McKeegan, K. D.

    2014-11-01

    The Cl isotope composition of martian meteorites range from -3.8 to +8.6 per mil. Ol-phyric shergottites are lightest; crustally contaminated samples are heaviest, basaltic shergottites are in-between. The system is explained as two component mixing.

  6. Sulfur-based absolute quantification of proteins using isotope dilution inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Lee, Hyun-Seok; Heun Kim, Sook; Jeong, Ji-Seon; Lee, Yong-Moon; Yim, Yong-Hyeon

    2015-10-01

    An element-based reductive approach provides an effective means of realizing International System of Units (SI) traceability for high-purity biological standards. Here, we develop an absolute protein quantification method using double isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS) combined with microwave-assisted acid digestion for the first time. We validated the method and applied it to certify the candidate protein certified reference material (CRM) of human growth hormone (hGH). The concentration of hGH was determined by analysing the total amount of sulfur in hGH. Next, the size-exclusion chromatography method was used with ICP-MS to characterize and quantify sulfur-containing impurities. By subtracting the contribution of sulfur-containing impurities from the total sulfur content in the hGH CRM, we obtained a SI-traceable certification value. The quantification result obtained with the present method based on sulfur analysis was in excellent agreement with the result determined via a well-established protein quantification method based on amino acid analysis using conventional acid hydrolysis combined with an ID liquid chromatography-tandem mass spectrometry. The element-based protein quantification method developed here can be generally used for SI-traceable absolute quantification of proteins, especially pure-protein standards.

  7. Carbonate abundances and isotopic compositions in chondrites

    NASA Astrophysics Data System (ADS)

    Alexander, C. M. O'd.; Bowden, R.; Fogel, M. L.; Howard, K. T.

    2015-04-01

    We report the bulk C abundances, and C and O isotopic compositions of carbonates in 64 CM chondrites, 14 CR chondrites, 2 CI chondrites, LEW 85332 (C2), Kaba (CV3), and Semarkona (LL3.0). For the unheated CMs, the total ranges of carbonate isotopic compositions are δ13C ≈ 25-75‰ and δ18O ≈ 15-35‰, and bulk carbonate C contents range from 0.03 to 0.60 wt%. There is no simple correlation between carbonate abundance and isotopic composition, or between either of these parameters and the extent of alteration. Unless accretion was very heterogeneous, the uncorrelated variations in extent of alteration and carbonate abundance suggests that there was a period of open system behavior in the CM parent body, probably prior to or at the start of aqueous alteration. Most of the ranges in CM carbonate isotopic compositions can be explained by their formation at different temperatures (0-130 °C) from a single fluid in which the carbonate O isotopes were controlled by equilibrium with water (δ18O ≈ 5‰) and the C isotopes were controlled by equilibrium with CO and/or CH4 (δ13C ≈ -33‰ or -20‰ for CO- or CH4-dominated systems, respectively). However, carbonate formation would have to have been inefficient, otherwise carbonate compositions would have resembled those of the starting fluid. A quite similar fluid composition (δ18O ≈ -5.5‰, and δ13C ≈ -31‰ or -17‰ for CO- or CH4-dominated systems, respectively) can explain the carbonate compositions of the CIs, although the formation temperatures would have been lower (~10-40 °C) and the relative abundances of calcite and dolomite may play a more important role in determining bulk carbonate compositions than in the CMs. The CR carbonates exhibit a similar range of O isotopes, but an almost bimodal distribution of C isotopes between more (δ13C ≈ 65-80‰) and less altered samples (δ13C ≈ 30-40‰). This bimodality can still be explained by precipitation from fluids with the same isotopic

  8. Isotopic composition of Silurian seawater

    SciTech Connect

    Knauth, L.P.; Kealy, S.; Larimer, S.

    1985-01-01

    Direct isotopic analyses of 21 samples of the Silurian hydrosphere preserved as fluid inclusions in Silurian halite deposits in the Michigan Basin Salina Group yield delta/sup 18/O, deltaD ranging from 0.2 to +5.9 and -26 to -73, respectively. delta/sup 18/O has the same range as observed for modern halite facies evaporite waters and is a few per thousand higher than 100 analyses of fluid inclusions in Permian halite. deltaD is about 20 to 30 per thousand lower than modern and Permian examples. The trajectory of evaporating seawater on a deltaD-delta/sup 18/O diagram initially has a positive slope of 3-6, but hooks strongly downward to negative values, the shape of the hook depending upon humidity. Halite begins to precipitate at delta values similar to those observed for the most /sup 18/O rich fluid inclusions. Subsequent evaporation yields progressively more negative delta values as observed for the fluid inclusions. The fluid inclusion data can be readily explained in terms of evaporating seawater and are consistent with the degree of evaporation deduced from measured bromide profiles. These data are strongly inconsistent with arguments that Silurian seawater was 5.5 per thousand depleted in /sup 18/O. delta/sup 18/O for evaporite waters is systematically related to that of seawater, and does not show a -5.5 per thousand shift in the Silurian, even allowing for variables which affect the isotope evaporation trajectory. The lower deltaD may indicate a component of gypsum dehydration waters or may suggest a D-depleted Silurian hydrosphere.

  9. The Cu isotopic composition of iron meteorites

    NASA Astrophysics Data System (ADS)

    Bishop, Matthew Cole; Moynier, Frederic; Weinstein, Charlotte; Fraboulet, Jean-Gabriel; Wang, Kun; Foriel, Julien

    2012-02-01

    High-precision Cu isotopic compositions have been measured for the metal phase of 29 iron meteorites from various groups and for four terrestrial standards. The data are reported as the δ65Cu permil deviation of the 65Cu/63Cu ratio relative to the NIST SRM 976 standard. Terrestrial mantle rocks have a very narrow range of variations and scatter around zero. In contrast, iron meteorites show δ65Cu approximately 2.3‰ variations. Different groups of iron meteorites have distinct δ65Cu values. Nonmagmatic IAB-IIICD iron meteorites have similar δ65Cu (0.03 ± 0.08 and 0.12 ± 0.10, respectively), close to terrestrial values (approximately 0). The other group of nonmagmatic irons, IIE, is isotopically distinct (-0.69 ± 0.15). IVB is the iron meteorite group with the strongest elemental depletion in Cu and samples in this group are enriched in the lighter isotope (δ65Cu down to -2.26‰). Evaporation should have produced an enrichment in 65Cu over 63Cu (δ65Cu >0) and can therefore be ruled out as a mechanism for volatile loss in IVB meteorites. In silicate-bearing iron meteorites, Δ17O correlates with δ65Cu. This correlation between nonmass-dependent and mass-dependent parameters suggests that the Cu isotopic composition of iron meteorites has not been modified by planetary differentiation to a large extent. Therefore, Cu isotopic ratios can be used to confirm genetic links. Cu isotopes thus confirm genetic relationships between groups of iron meteorites (e.g., IAB and IIICD; IIIE and IIIAB); and between iron meteorites and chondrites (e.g., IIE and H chondrites). Several genetic connections between iron meteorites groups are confirmed by Cu isotopes, (e.g., IAB and IIICD; IIIE and IIIAB); and between iron meteorites and chondrites (e.g., IIE and H chondrites).

  10. Isotopic composition of precipitation in Greece

    NASA Astrophysics Data System (ADS)

    Argiriou, Athanassios A.; Lykoudis, Spyros

    2006-08-01

    SummaryThe contribution of stable isotopes in meteorological, climatological and hydrological research is well known. Until this date and despite the fact that several hydrological studies of water sources in Greece have been published, no systematic isotopic study of precipitation has been performed in the country. This paper presents all the available isotopic data collected since 1960 in several Hellenic measurement stations. This data is divided in two periods: the first covers data that was collected in the past, in the frame of a preliminary survey of the isotope composition of precipitation in the Eastern Mediterranean Sea and specific hydrological studies; the second is the result of a three-year coordinated research project of the International Atomic Energy Agency, in which the authors participated, aiming at the systematic study of stable isotopes ( 2H and 18O) and 3H in precipitation around the Mediterranean basin. No statistically significant behavior between the two periods of data was found. The isotopic content of precipitation presents characteristics intermediate of those of the Eastern and Western Mediterranean. The tritium concentration in precipitation declines as expected towards the pre-bomb levels, however there is an indication that tritium concentrations are higher in Northern Greece.

  11. Some triple-filament lead isotope ratio measurements and an absolute growth curve for single-stage leads

    USGS Publications Warehouse

    Stacey, J.S.; Delevaux, M.E.; Ulrych, T.J.

    1969-01-01

    Triple-filament analyses of three standard lead samples are used to calibrate a mass spectrometer in an absolute sense. The bias we measure is 0.0155 percent per mass unit, and the precision (for 95% confidence limits) is ??0.13% or less for all ratios relative to 204Pb. Although its precision is not quite so good as that of the lead-tetramethyl method in the analysis of large samples, the triple-filament method is less complex and is an attractive alternative for smaller sample sizes down to 500 ??g. Triple-filament data are presented for six possibly single-stage lead ores and one feldspar. These new data for ores are combined with corrected tetramethyl data for stratiform lead deposits to compute absolute parameters for a universal single-stage lead isotope growth curve. Absolute isotopic ratios for primeval lead have been determined by Oversby and because all the previous data for both meteorites and lead ores were similarly fractionated, the absolute value of 238U 204Pb = 9.09 ?? 0.06 for stratiform leads is little different from the value 8.99 ?? 0.05 originally computed by Ostic, Russell and Stanton. Absolute values for lead isotope ratios for all interlaboratory standard samples presently available from the literature are tabulated. ?? 1969.

  12. Tungsten Stable Isotope Compositions of Ferromanganese Crusts

    NASA Astrophysics Data System (ADS)

    Abraham, K.; Barling, J.; Hein, J. R.; Schauble, E. A.; Halliday, A. N.

    2014-12-01

    We report the first accurate and precise data for mass-dependent fractionation of tungsten (W) stable isotopes, using a double spike technique and MC-ICPMS. Results are expressed relative to the NIST 3136 W isotope standard as per mil deviations in 186W/184W (δ186W). Although heavy element mass-dependent fractionations are expected to be small, Tl and U both display significant low temperature isotopic fractionations. Theoretical calculations indicate that W nuclear volume isotopic effects should be smaller than mass-dependent fractionations at low temperatures. Hydrogenetic ferromanganese (Fe-Mn) crusts precipitate directly from seawater and have been used as paleoceanographic recorders of temporal changes in seawater chemistry. Crusts are strongly enriched in W and other metals, and are a promising medium for exploring W isotopic variability. Tungsten has a relatively long residence time in seawater of ~61,000 years, mainly as the tungstate ion (WO42-). Water depth profiles show conservative behaviour. During adsorption on Fe-Mn crusts, W species form inner-sphere complexes in the hexavalent (W6+) state. The major host phase is thought to be Mn oxides and the lighter W isotope is expected to be absorbed preferentially. Surface scrapings of 13 globally distributed hydrogenetic Fe-Mn crusts display δ186W from -0.08 to -0.22‰ (±0.03‰, 2sd). A trend toward lighter W isotope composition exists with increasing water depth (~1500 to ~5200m) and W concentration. One hydrothermal Mn-oxide sample is anomalously light and Mn nodules are both heavy and light relative to Fe-Mn crusts. Tungsten speciation depends on concentration, pH, and time in solution and is not well understood because of the extremely slow kinetics of the reactions. In addition, speciation of aqueous and/or adsorbed species might be sensitive to pressure, showing similar thermodynamic stability but different effective volumes. Thus, W stable isotopes might be used as a water-depth barometer in

  13. Isotopic Composition of Oxygen in Lunar Zircons

    NASA Technical Reports Server (NTRS)

    Nemchin, A. A.; Whitehouse, M. J.; Pidgeon, R. T.; Meyer, C.

    2005-01-01

    The recent discovery of heavy oxygen in zircons from the Jack Hills conglomerates Wilde et al. and Mojzsis et al. was interpreted as an indication of presence of liquid water on the surface of Early Earth. The distribution of ages of Jack Hills zircons and lunar zircons appears to be very similar and therefore analysis of oxygen in the lunar grains may provide a reference frame for further study of the early history of the Earth as well as give additional information regarding processes that operated on the Moon. In the present study we have analysed the oxygen isotopic composition of zircon grains from three lunar samples using the Swedish Museum of Natural History CAMECA 1270 ion microprobe. The samples were selected as likely tests for variations in lunar oxygen isotopic composition. Additional information is included in the original extended abstract.

  14. ISOTOPIC COMPOSITIONS OF URANIUM REFERENCE MATERIALS

    SciTech Connect

    Jacobsen, B; Borg, L; Williams, R; Brennecka, G; Hutcheon, I

    2009-09-03

    Uranium isotopic compositions of a variety of U standard materials were measured at Lawrence Livermore National Laboratory and are reported here. Both thermal ionization mass spectrometry (TIMS) and multi-collector inductively couple plasma mass spectrometry (MC-ICPMS) were used to determine ratios of the naturally occurring isotopes of U. Establishing an internally coherent set of isotopic values for a range of U standards is essential for inter-laboratory comparison of small differences in {sup 238}U/{sup 235}U, as well as the minor isotopes of U. Differences of {approx} 1.3{per_thousand} are now being observed in {sup 238}U/{sup 235}U in natural samples, and may play an important role in understanding U geochemistry where tracing the origin of U is aided by U isotopic compositions. The {sup 238}U/{sup 235}U ratios were measured with a TRITON TIMS using a mixed {sup 233}U-{sup 236}U isotopic tracer to correct for instrument fractionation. this tracer was extremely pure and resulted in only very minor corrections on the measured {sup 238}U/{sup 235}U ratios of {approx} 0.03. The values obtained for {sup 238}U/{sup 235}U are: IRMM184 = 137.698 {+-} 0.020 (n = 15), SRM950a = 137.870 {+-} 0.018 (n = 8), and CRM112a = 137.866 {+-} 0.030 (n = 16). Uncertainties represent 2 s.d. of the population. The measured value for IRMM184 is in near-perfect agreement with the certified value of 137.697 {+-} 0.042. However, the U isotopic compositions of SRM950a and CRM112a are not certified. Minor isotopes of U were determined with a Nu Plasma HR MC-ICPMS and mass bias was corrected by sample/standard bracketing to IRMM184, using its certified {sup 238}U/{sup 235}U ratio. Thus, the isotopic compositions determined using both instruments are compatible. The values obtained for {sup 234}U/{sup 235}U are: SRM950a = (7.437 {+-} 0.043) x 10{sup -3} (n = 18), and CRM112a = (7.281 {+-} 0.050) x 10{sup -3} (n = 16), both of which are in good agreement with published values. The value for

  15. Advances in the Metrology of Absolute Value Assignments to Isotopic Reference Materials: Consequences from the Avogadro Project

    NASA Astrophysics Data System (ADS)

    Vocke, Robert; Rabb, Savelas

    2015-04-01

    All isotope amount ratios (hereafter referred to as isotope ratios) produced and measured on any mass spectrometer are biased. This unfortunate situation results mainly from the physical processes in the source area where ions are produced. Because the ionized atoms in poly-isotopic elements have different masses, such processes are typically mass dependent and lead to what is commonly referred to as mass fractionation (for thermal ionization and electron impact sources) and mass bias (for inductively coupled plasma sources.) This biasing process produces a measured isotope ratio that is either larger or smaller than the "true" ratio in the sample. This has led to the development of numerous fractionation "laws" that seek to correct for these effects, many of which are not based on the physical processes giving rise to the biases. The search for tighter and reproducible precisions has led to two isotope ratio measurement systems that exist side-by-side. One still seeks to measure "absolute" isotope ratios while the other utilizes an artifact based measurement system called a delta-scale. The common element between these two measurement systems is the utilization of isotope reference materials (iRMs). These iRMs are used to validate a fractionation "law" in the former case and function as a scale anchor in the latter. Many value assignments of iRMs are based on "best measurements" by the original groups producing the reference material, a not entirely satisfactory approach. Other iRMs, with absolute isotope ratio values, have been produced by calibrated measurements following the Atomic Weight approach (AW) pioneered by NBS nearly 50 years ago. Unfortunately, the AW is not capable of calibrating the new generation of iRMs to sufficient precision. So how do we get iRMs with isotope ratios of sufficient precision and without bias? Such a focus is not to denigrate the extremely precise delta-scale measurements presently being made on non-traditional and tradition

  16. Sulfur Isotope Composition of Putative Primary Troilite in Chondrules

    NASA Technical Reports Server (NTRS)

    Tachibana, Shogo; Huss, Gary R.

    2002-01-01

    Sulfur isotope compositions of putative primary troilites in chondrules from Bishunpur were measured by ion probe. These primary troilites have the same S isotope compositions as matrix troilites and thus appear to be isotopically unfractionated. Additional information is contained in the original extended abstract.

  17. The Oxygen Isotopic Composition of the Sun

    NASA Astrophysics Data System (ADS)

    McKeegan, K. D.; Kallio, A.; Heber, V. S.; Jarzebinski, G.; Mao, P.; Coath, C.; Kunihiro, T.; Wiens, R. C.; Judith, A.; Burnett, D. S.

    2010-12-01

    An accurate and precise determination of the oxygen isotopic composition of the Sun is the highest priority scientific goal of the Genesis Mission [1] as such data would provide a baseline from which one could interpret the oxygen isotopic anomalies found at all spatial scales in inner solar system materials. We have measured oxygen isotope compositions of implanted solar wind in 40 spots along a radial traverse of the Genesis SiC target sample 60001 by depth profiling with the UCLA MegaSIMS [2]. Mass-dependent fractionation induced by the solar wind concentrator [3] ion optics was corrected by comparison of the concentrator 22Ne/20Ne with that measured in a bulk solar wind target (diamond-like carbon on Si, [4]). The solar wind captured at L1 has an isotopic composition of (δ18O, δ17O) ≈ (-99, -79)‰, a value which is far removed from the terrestrial mass fractionation line. Profiles from the central portion of the target, where solar concentrations are highest and background corrections minimal, yield a mean Δ17O = -28.3 ± 1.8 ‰ indicating that the Earth and other planetary materials from the inner solar system are highly depleted in 16O relative to the solar wind. A mass-dependent fractionation of ~ -20%/amu in the acceleration of solar wind is required if we hypothesize that the photospheric oxygen isotope value, which represents the bulk starting composition of the solar system, is on the 16O-mixing line characteristic of refractory phase in primitive meteorites [5]. With this assumption, our preferred value for the bulk solar oxygen isotope composition is δ18O ≈ δ17O ≈ -57‰. A mechanism is required to fractionate oxygen isotopes in a non-mass-dependent manner to deplete 16O by ~6 to 7% in the rocky materials of the solar nebula. As oxygen is the third most abundant element in the solar system, and the most abundant in the terrestrial planets, this mechanism must operate on a large scale. Isotope-selective photochemistry, for example as in

  18. THE NITROGEN ISOTOPIC COMPOSITION OF METEORITIC HCN

    SciTech Connect

    Pizzarello, Sandra

    2014-12-01

    HCN is ubiquitous in extraterrestrial environments and is central to current theories on the origin of early solar system organic compounds such as amino acids. These compounds, observed in carbonaceous meteorites, were likely important in the origin and/or evolution of early life. As part of our attempts to understand the origin(s) of meteoritic CN{sup –}, we have analyzed the {sup 15}N/{sup 14}N isotopic composition of HCN gas released from water extracts of the Murchison meteorite and found its value to be near those of the terrestrial atmosphere. The findings, when evaluated viz-a-viz molecular abundances and isotopic data of meteoritic organic compounds, suggest that HCN formation could have occurred during the protracted water alteration processes known to have affected the mineralogy of many asteroidal bodies during their solar residence. This was an active synthetic stage, which likely involved simple gasses, organic molecules, their presolar precursors, as well as mineral catalysts and would have lead to the formation of molecules of differing isotopic composition, including some with solar values.

  19. Cadmium isotopic composition in the ocean

    NASA Astrophysics Data System (ADS)

    Lacan, Francois; Francois, Roger; Ji, Yongcheng; Sherrell, Robert M.

    2006-10-01

    The oceanic cycle of cadmium is still poorly understood, despite its importance for phytoplankton growth and paleoceanographic applications. As for other elements that are biologically recycled, variations in isotopic composition may bring unique insights. This article presents (i) a protocol for the measurement of cadmium isotopic composition (Cd IC) in seawater and in phytoplankton cells; (ii) the first Cd IC data in seawater, from two full depth stations, in the northwest Pacific and the northwest Mediterranean Sea; (iii) the first Cd IC data in phytoplankton cells, cultured in vitro. The Cd IC variation range in seawater found at these stations is not greater than 1.5 ɛCd/amu units, only slightly larger than the mean uncertainty of measurement (0.8 ɛCd/amu). Nevertheless, systematic variations of the Cd IC and concentration in the upper 300 m of the northwest Pacific suggest the occurrence of Cd isotopic fractionation by phytoplankton uptake, with a fractionation factor of 1.6 ± 1.4 ɛCd/amu units. This result is supported by the culture experiment data suggesting that freshwater phytoplankton ( Chlamydomonas reinhardtii and Chlorella sp.) preferentially take up light Cd isotopes, with a fractionation factor of 3.4 ± 1.4 ɛCd/amu units. Systematic variations of the Cd IC and hydrographic data between 300 and 700 m in the northwest Pacific have been tentatively attributed to the mixing of the mesothermal (temperature maximum) water ( ɛCd/amu = -0.9 ± 0.8) with the North Pacific Intermediate Water ( ɛCd/amu = 0.5 ± 0.8). In contrast, no significant Cd IC variation is found in the northwest Mediterranean Sea. This observation was attributed to the small surface Cd depletion by phytoplankton uptake and the similar Cd IC of the different water masses found at this site. Overall, these data suggest that (i) phytoplankton uptake fractionates Cd isotopic composition to a measurable degree (fractionation factors of 1.6 and 3.4 ɛCd/amu units, for the in situ and

  20. Oxygen isotope composition of trinitite postdetonation materials.

    PubMed

    Koeman, Elizabeth C; Simonetti, Antonio; Chen, Wei; Burns, Peter C

    2013-12-17

    Trinitite is the melt glass produced subsequent the first nuclear bomb test conducted on July 16, 1945, at White Sands Range (Alamagordo, NM). The geological background of the latter consists of arkosic sand that was fused with radioactive debris and anthropogenic materials at ground zero subsequent detonation of the device. Postdetonation materials from historic nuclear weapon test sites provide ideal samples for development of novel forensic methods for attribution and studying the chemical/isotopic effects of the explosion on the natural geological environment. In particular, the latter effects can be evaluated relative to their spatial distribution from ground zero. We report here δ(18)O(‰) values for nonmelted, precursor minerals phases (quartz, feldspar, calcite), "feldspathic-rich" glass, "average" melt glass, and bulk (natural) unmelted sand from the Trinity site. Prior to oxygen isotope analysis, grains/crystals were examined using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) to determine their corresponding major element composition. δ(18)O values for bulk trinitite samples exhibit a large range (11.2-15.5‰) and do not correlate with activity levels for activation product (152)Eu; the latter levels are a function of their spatial distribution relative to ground zero. Therefore, the slow neutron flux associated with the nuclear explosion did not perturb the (18)O/(16)O isotope systematics. The oxygen isotope values do correlate with the abundances of major elements derived from precursor minerals present within the arkosic sand. Hence, the O isotope ratios documented here for trinitite melt glass can be attributed to a mixture of the respective signatures for precursor minerals at the Trinity site prior to the nuclear explosion. PMID:24304329

  1. Mg Isotopic Compositions of Modern Marine Carbonates

    NASA Astrophysics Data System (ADS)

    Krogstad, E.; Bizzarro, M.; Hemming, N.

    2003-12-01

    We have used a MC-ICP-MS to measure the isotopic composition of magnesium in a number of samples of modern marine carbonate. Due to the large mass difference between 26Mg and 24Mg (similar to that between 13C and 12C), there is potential for mass fractionation during geologic and biologic processes that may make this isotope system useful for geochemical studies. These samples are from the study of Hemming and Hanson (1992, GCA 56: 537-543). The carbonate minerals analyzed include aragonite, low-Mg calcite, and high-Mg calcite. The samples include corals, echinoderms, ooids, etc., from subtropical to Antarctic settings. Mg purification was accomplished by ion-exchange chromatography, using Bio-Rad AG50W-X12 resin on which greater than 99 percent recovery of Mg is achieved. Samples were introduced into the MC-ICP-MS (VG Axiom) using a Cetac MCN-6000 nebuliser. We use a standard-sample-standard bracketing technique, and samples are analysed at least three times. For lab standards we find that the reproducibility on the 26Mg/24Mg to be about ñ 0.12 permil (2 s.d.). We monitored our separated samples for Na and Ca, as we have found that high Ca/Mg and Na/Mg produce variable magnesium isotopic fractionation during mass spectrometry due to as yet unclear matrix effects. We have normalized our results to our measured values for seawater. We observed a d26Mg(s.w.) range of -1.4 to -2.4 permil in our modern carbonate samples relative to present day seawater. Due to the long residence time of Mg in the oceans (ca. 50 my), this must be due to kinetic or biologic effects. Our d25Mg(s.w.) variations as a function of d26Mg(s.w.) plot along the terrestrial fractionation trend. With an average d26Mg(s.w.) of ca. +0.5 permil in all samples of mantle lithologies and mantle-derived igneous rocks (Bizzarro et al., Goldschmidt abs., 2003), we can assume that the Mg isotopic composition of Earth's river water lies between ca. -2.4 and +0.5 permil (relative to seawater). The actual

  2. Isotopic composition of Riyadh rainfall, Saudi Arabia

    NASA Astrophysics Data System (ADS)

    Michelsen, Nils; Reshid, Mustefa; Siebert, Christian; Schulz, Stephan; Rausch, Randolf; Knöller, Kay; Weise, Stephan; Al-Saud, Mohammed; Schüth, Christoph

    2015-04-01

    Arid countries like Saudi Arabia often depend on fossil groundwater. Hence, thorough studies of the available resources are crucial. In the course of such investigations, analyses of δ18O and δD are frequently applied to constrain the provenance of the waters and to reconstruct the (paleo)climatic conditions during their recharge. Yet, to be able to evaluate the isotopic signature of the groundwater, one also has to know the isotopic composition of current precipitation. Although a few rain water analyses are available for Central Saudi Arabia in the literature - mostly in unpublished consultant reports - a Local Meteoric Water Line has never been established. To complement the available data, 28 rain events occurring in Riyadh between 2009 and 2013 were studied for their stable isotope composition. Samples were collected as integral samples, i.e., they represent the entire precipitation event. Moreover, one event was sampled several times, aiming at an evaluation of intra-storm variability. During selected storms, a grab sample was taken for 3H analysis. The event samples showed δ18O and δD values scattering between -6.5 and +9.5 and between -30 and +50 ‰ V-SMOW, respectively. In the course of the event that was sequentially sampled, a proceeding isotopic depletion was observed with respect to both isotopes. The relatively large ranges of δ-values for 18O and D of approximately 7 and 38 ‰ V-SMOW highlight the general need for integral sampling. The obtained grab samples are characterized by moderate 3H concentrations of a few Tritium Units. Further results will be presented and discussed in view of associated weather data (e.g. rain amount and temperature) and the probable moisture sources derived from back-trajectories, which were calculated using HYSPLIT (Hybrid Single-Particle Lagrangian Integrated Trajectory Model; Draxler & Rolph, 2003). References Draxler, R.R. & Rolph, G.D. (2013): HYSPLIT (Hybrid Single-Particle Lagrangian Integrated Trajectory

  3. Molybdenum Isotopic Composition of Iron Meteorites, Chondrites and Refractory Inclusions

    NASA Technical Reports Server (NTRS)

    Becker, H.; Walker, R. J.

    2003-01-01

    Recent Mo isotopic studies of meteorites reported evidence for differences in isotopic compositions for whole rocks of some primitive and differentiated meteorites relative to terrestrial materials. Enrichments of r- and p-process isotopes of up to 3-4 units (e unit = parts in 10(exp 4) over s-process dominated isotopes are the most prominent features. Certain types of presolar grains show large enrichments in s-process isotopes, however, it was concluded on grounds of mass balance that incomplete digestion of such grains cannot explain the enrichments of r- and p-process isotopes in whole rocks of primitive chondrites. If the reported variability in r- and p-process isotope enrichments reflects the true isotopic characteristics of the whole rocks, the implications are quite profound. It would suggest the presence of large scale Mo isotopic heterogeneity within the solar accretion disk with likely collateral effects for other elements. However, such effects were not found for Ru isotopes, nor for Zr isotopes. Another recent Mo isotopic study by multi collector ICP-MS could not confirm the reported deviations in Allende, Murchison or iron meteorites. Here, we present new results for the Mo isotopic composition of iron meteorites, chondrites and CAIs obtained by negative thermal ionization mass spectrometry (NTIMS). We discuss analytical aspects and the homogeneity of Mo isotopic compositions in solar system materials.

  4. Lithium Isotopic Composition of Aleutian Arc Magmas

    NASA Astrophysics Data System (ADS)

    Rudnick, R. L.; Park, Y.; Liu, X.; Kay, S. M.; Kay, R. W.

    2012-12-01

    The lithium isotopic compositions of inputs to subduction zones can be highly variable. For example, altered oceanic crust is isotopically heavy (δ7Li = 4 to 22, Chan et al., 1996; Bouman et al., 2004) due to uptake of seawater Li (32). Sea floor sediments can have highly variable compositions, ranging from isotopically heavy pelagic sediments (6 to 14) to isotopically light terrigneous clays (-1.5 to 5), derived from highly weathered continental crust (Chan et al., 2006). Despite this variability in inputs, arc outputs (magmatic rocks) typically have mantle-like δ7Li (e.g., 2 to 6; Tomascak et al., 2002; Walker et al., 2009). To explore the behavior of lithium and its isotopes in arcs, we have analyzed [Li] and δ7Li in 48 lavas and plutons from the Aleutian island arc, which span the temporal (0 to 38 Ma), geographical (165-184oW) and compositional variations (SiO2 = 46-70 wt.%) seen in this arc. Previous studies have indicated a systematic geographic change in lava chemistry related to changing sediment composition along the arc (terrigneous in the east, pelagic in the west, e.g., Kay and Kay, 1994; Yogodinski et al., 2010), as well as temporal changes that may also reflect changes in sedimentary input (Kay and Kay, 1994), and we wished to determine if Li isotopes also reflect such changes. Lithium concentration [Li] shows a generally positive correlation with SiO2, consistent with the expected incompatible behavior of Li during magmatic differentiation. Intrusive rocks (all from the Adak region) show more scatter than lavas on this plot, suggesting the influence of cumulate processes. The δ7Li of the rocks span an immense range from -1 to +29, well outside the values considered typical for the MORB-source mantle (e.g., 2-6). However, the majority of the samples (28 out of 48) have δ7Li falling within the range of typical mantle values. There is a general tendency for the lavas (all but one are <2 Ma) to have slightly lower δ7Li than intrusions (which range

  5. The Lithium Isotope Composition of Planktonic Foraminifera

    NASA Astrophysics Data System (ADS)

    Hathorne, E. C.; James, R. H.; Harris, N. B.

    2003-12-01

    The temporal record of the lithium isotopic composition of seawater has the potential to provide an important proxy of the relative rates of weathering and hydrothermal processes. One of the most powerful types of evidence for changes in ocean chemistry comes from analyses of foraminiferal calcium carbonate. Here, we explore the utility of foraminifera as recorders of the Li isotopic composition of seawater. The Li isotopic composition of foraminifera tests has been determined by multicollector inductively coupled plasma mass spectrometry (Nu Instruments) using a sample-standard bracketing technique. The external precision of this technique is +/- 0.3 ‰ (2σ ), based on fifteen analyses of seawater over a period of 9 months. Planktonic foraminifera ( ˜10 mg) have been picked from surface sediments of the equatorial Pacific and the North Atlantic. Samples from the equatorial Pacific are Holocene/Pleistocene in age; those from the North Atlantic are from the Holocene. The foraminifera were subject to; cleaning in methanol and water, oxidation (hydrogen peroxide and sodium hydroxide), and leaching in weak acid (0.001M nitric acid). Additional reductive and refractory-phase cleaning steps (respectively, hydrous hydrazine/ammonia and DTPA solutions) had no effect on δ 7Li or Li/Ca. The δ 7Li value of the foraminifera ranges from 27 to 31‰ ; slightly lighter than modern-day seawater (31.1 ‰ ). Different species have consistently different δ 7Li values; O. universa have δ 7Li values within error of seawater, while Gr. truncatulinoides record the lightest δ 7Li (27.1+/- 0.3‰ ). This indicates that there are species specific vital effects on foraminiferal δ 7Li. Samples of the same species from different latitudes in the North Atlantic have the same δ 7Li, suggesting that there is no temperature effect on foraminiferal δ 7Li. Furthermore, with the exception of G. sacculifer, there appears to be no variability in foraminiferal δ 7Li with test size

  6. Measurements of Isotopic Composition of Vapour on the Antarctic Plateau

    NASA Astrophysics Data System (ADS)

    Casado, M.; Landais, A.; Masson-Delmotte, V.; Genthon, C.; Prie, F.; Kerstel, E.; Kassi, S.; Arnaud, L.; Steen-Larsen, H. C.; Vignon, E.

    2015-12-01

    The oldest ice core records are obtained on the East Antarctic plateau. The composition in stable isotopes of water (δ18O, δD, δ17O) permits to reconstruct the past climatic conditions over the ice sheet and also at the evaporation source. Paleothermometer accuracy relies on good knowledge of processes affecting the isotopic composition of surface snow in Polar Regions. Both simple models such as Rayleigh distillation and global atmospheric models with isotopes provide good prediction of precipitation isotopic composition in East Antarctica but post deposition processes can alter isotopic composition on site, in particular exchanges with local vapour. To quantitatively interpret the isotopic composition of water archived in ice cores, it is thus essential to study the continuum water vapour - precipitation - surface snow - buried snow. While precipitation and snow sampling are routinely performed in Antarctica, climatic conditions in Concordia, very cold (-55°C in average) and very dry (less than 1000ppmv), impose difficult conditions to measure the water vapour isotopic composition. New developments in infrared spectroscopy enable now the measurement of isotopic composition in water vapour traces (down to 20ppmv). Here we present the results of a campaign of measurement of isotopic composition in Concordia in 2014/2015. Two infrared spectrometers have been deployed or the first time on top of the East Antarctic Plateau allowing a continuous vapour measurement for a month. Comparison of the results from infrared spectroscopy with cryogenic trapping validates the relevance of the method to measure isotopic composition in dry conditions. Identification of different behaviour of isotopic composition in the water vapour associated to turbulent or stratified regime indicates a strong impact of meteorological processes in local vapour/snow interaction.

  7. Morphology Composition Isotopes: Recent Results from Observations

    NASA Astrophysics Data System (ADS)

    Schulz, R.

    2008-07-01

    This article presents some recent imaging and spectroscopic observations that led to results which are significant for understanding the properties of comet nuclei. The coma morphology and/or composition were investigated for 12 comets belonging to different dynamical classes. The data analysis showed that the coma morphology of three non-periodic comets is not consistent with the general assumption that dynamically new comets still have a relatively uniform nucleus surface and therefore do not exhibit gas and/or dust jets in their coma. The determination of carbon and nitrogen isotopic ratios revealed the same values for all comets investigated at various heliocentric distances. However, the relative abundance of the rare nitrogen isotope 15N is about twice as high as in the Earth’s atmosphere. Observations of comets at splitting events and during outbursts led to indications for differences between material from the nucleus surface and the interior. The monitoring of the induced outburst of 9P/Temple revealed that under non-steady state conditions the fast disintegration of species is detectable.

  8. Peptide Biosynthesis with Stable Isotope Labeling from a Cell-free Expression System for Targeted Proteomics with Absolute Quantification.

    PubMed

    Xian, Feng; Zi, Jin; Wang, Quanhui; Lou, Xiaomin; Sun, Haidan; Lin, Liang; Hou, Guixue; Rao, Weiqiao; Yin, Changcheng; Wu, Lin; Li, Shuwei; Liu, Siqi

    2016-08-01

    Because of its specificity and sensitivity, targeted proteomics using mass spectrometry for multiple reaction monitoring is a powerful tool to detect and quantify pre-selected peptides from a complex background and facilitates the absolute quantification of peptides using isotope-labeled forms as internal standards. How to generate isotope-labeled peptides remains an urgent challenge for accurately quantitative targeted proteomics on a large scale. Herein, we propose that isotope-labeled peptides fused with a quantitative tag could be synthesized through an expression system in vitro, and the homemade peptides could be enriched by magnetic beads with tag-affinity and globally quantified based on the corresponding multiple reaction monitoring signals provided by the fused tag. An Escherichia coli cell-free protein expression system, protein synthesis using recombinant elements, was adopted for the synthesis of isotope-labeled peptides fused with Strep-tag. Through a series of optimizations, we enabled efficient expression of the labeled peptides such that, after Strep-Tactin affinity enrichment, the peptide yield was acceptable in scale for quantification, and the peptides could be completely digested by trypsin to release the Strep-tag for quantification. Moreover, these recombinant peptides could be employed in the same way as synthetic peptides for multiple reaction monitoring applications and are likely more economical and useful in a laboratory for the scale of targeted proteomics. As an application, we synthesized four isotope-labeled glutathione S-transferase (GST) peptides and added them to mouse sera pre-treated with GST affinity resin as internal standards. A quantitative assay of the synthesized GST peptides confirmed the absolute GST quantification in mouse sera to be measurable and reproducible. PMID:27234506

  9. Magnesium Isotopic Composition of Subducting Marine Sediments

    NASA Astrophysics Data System (ADS)

    Hu, Y.; Teng, F. Z.; Plank, T. A.; Huang, K. J.

    2015-12-01

    Subducted marine sediments have recently been called upon to explain the heterogeneous Mg isotopic composition (δ26Mg, ‰) found in mantle wehrlites (-0.39 to +0.09 [1]) in the context of a homogeneous mantle (-0.25 ± 0.07 [2]). However, no systematic measurements of δ26Mg on marine sediments are currently available to provide direct support to this model. To characterize the Mg inputs to global subduction zones, we measured δ26Mg data for a total of 90 marine sediments collected from 12 drill sites outboard of the world's major subduction zones. These sediments span a 1.73‰ range in δ26Mg. The detritus-dominated sediments have δ26Mg (-0.59 to +0.53) comparable to those of weathered materials on continents (e.g. -0.52 to +0.92 [3]), while the calcareous oozes yield δ26Mg (as light as -1.20) more similar to the seawater value (-0.83 [4]). The negative correlation between δ26Mg and CaO/Al2O3 in these sediments indicates the primary control of mineralogy over the Mg isotopic distribution among different sediment types, as carbonates are enriched in light Mg isotopes (-5.10 to -0.40 [5]) whereas clay-rich weathering residues generally have heavier δ26Mg (e.g. up to +0.65 in saprolite [6]). In addition, chemical weathering and grain-size sorting drive sediments to a heavier δ26Mg, as indicated by the broad positive trends between δ26Mg with CIA (Chemical Index of Alteration [7]) and Al2O3/SiO2, respectively. Collectively, the arc systems sampled in this study represent ~30% of global arc length and the extrapolated global Mg flux of subducting marine sediments accounts for ~9% of the yearly Mg riverine input with a flux-weighted average δ26Mg at -0.26. Subduction of these heterogeneous sediments may not cause significant mantle heterogeneity on a global scale, but the highly variable Mg fluxes and δ26Mg of sediments delivered to different trenches are capable of producing local mantle variations. Volcanic rocks sourced from these mantle domains are thus

  10. The isotopic composition of Nd in different ocean masses

    NASA Technical Reports Server (NTRS)

    Piepgras, D. J.; Wasserburg, G. J.; Dasch, E. J.

    1979-01-01

    The paper examines the isotopic composition of Nd in marine environments. The Sm-Nd data for authigenic ferromanganese sediments indicate that the Atlantic, Pacific, and Indian Oceans have a distinct range in Nd isotopic composition characteristics of each ocean basin and reflect the dissolved load of Nd in the water mass. Measurements of the Nd isotopic seawater composition of seawater indicate that the rare earth elements (REE) in ferromanganese sediments are derived by direct precipitation of these elements out of seawater. It is believed that the Nd isotopic variations in these sediments represent true variations in the dissolved Nd isotopic composition which reflect the age and (Sm-147)/(Nd-144) ratios of the continental masses sampled believed to be the major source of REE in seawater.

  11. Magnesium isotopic composition of the Earth and chondrites

    NASA Astrophysics Data System (ADS)

    Teng, Fang-Zhen; Li, Wang-Ye; Ke, Shan; Marty, Bernard; Dauphas, Nicolas; Huang, Shichun; Wu, Fu-Yuan; Pourmand, Ali

    2010-07-01

    To constrain further the Mg isotopic composition of the Earth and chondrites, and investigate the behavior of Mg isotopes during planetary formation and magmatic processes, we report high-precision (±0.06‰ on δ 25Mg and ±0.07‰ on δ 26Mg, 2SD) analyses of Mg isotopes for (1) 47 mid-ocean ridge basalts covering global major ridge segments and spanning a broad range in latitudes, geochemical and radiogenic isotopic compositions; (2) 63 ocean island basalts from Hawaii (Kilauea, Koolau and Loihi) and French Polynesia (Society Island and Cook-Austral chain); (3) 29 peridotite xenoliths from Australia, China, France, Tanzania and USA; and (4) 38 carbonaceous, ordinary and enstatite chondrites including 9 chondrite groups (CI, CM, CO, CV, L, LL, H, EH and EL). Oceanic basalts and peridotite xenoliths have similar Mg isotopic compositions, with average values of δ 25Mg = -0.13 ± 0.05 (2SD) and δ 26Mg = -0.26 ± 0.07 (2SD) for global oceanic basalts ( n = 110) and δ 25Mg = -0.13 ± 0.03 (2SD) and δ 26Mg = -0.25 ± 0.04 (2SD) for global peridotite xenoliths ( n = 29). The identical Mg isotopic compositions in oceanic basalts and peridotites suggest that equilibrium Mg isotope fractionation during partial melting of peridotite mantle and magmatic differentiation of basaltic magma is negligible. Thirty-eight chondrites have indistinguishable Mg isotopic compositions, with δ 25Mg = -0.15 ± 0.04 (2SD) and δ 26Mg = -0.28 ± 0.06 (2SD). The constancy of Mg isotopic compositions in all major types of chondrites suggest that primary and secondary processes that affected the chemical and oxygen isotopic compositions of chondrites did not significantly fractionate Mg isotopes. Collectively, the Mg isotopic composition of the Earth's mantle, based on oceanic basalts and peridotites, is estimated to be -0.13 ± 0.04 for δ 25Mg and -0.25 ± 0.07 for δ 26Mg (2SD, n = 139). The Mg isotopic composition of the Earth, as represented by the mantle, is similar to chondrites

  12. Chemical composition, olfactory evaluation and antimicrobial activity of selected essential oils and absolutes from Morocco.

    PubMed

    Wanner, Juergen; Schmidt, Erich; Bail, Stefanie; Jirovetz, Leopold; Buchbauer, Gerhard; Gochev, Velizar; Girova, Tanya; Atanasova, Teodora; Stoyanova, Albena

    2010-09-01

    The chemical compositions of selected essential oils from North Africa, especially Morocco, of geranium, wild Moroccan chamomile and rosemary as well as absolutes of rose and geranium were determined using GC/FID and GC/MS. These oils and absolutes were tested concerning their antimicrobial activity against some food spoilage strains obtained from fresh milk and minced meat products, like sausages and pork fillet, in accordance with ISO testing procedures. Gram-positive (Bacillus cereus and Staphylococcus aureus) and Gram-negative (Escherichia coli, Salmonella abony and Pseudomonas aeruginosa) strains were used, as well as the yeast Candida albicans. Using a serial broth dilution method, all samples demonstrated weak antimicrobial activity against the Gram-negative bacteria and the yeast, compared with the activity towards the Gram-positive bacteria. PMID:20922989

  13. The Chlorine Isotopic Composition of Lunar urKREEP

    NASA Astrophysics Data System (ADS)

    Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

    2016-05-01

    We have measured the Cl isotopic composition of apatite in a range of lunar rocks using NanoSIMS. We find a correlation between Cl isotopes and bulk rock chemistry which strongly suggesting urKREEP was characterized by heavy Cl.

  14. Oxygen isotopic composition of hydrous and anhydrous mantle peridotites

    NASA Astrophysics Data System (ADS)

    Chazot, Gilles; Lowry, David; Menzies, Martin; Mattey, David

    1997-01-01

    Oxygen isotope ratios, determined using the laser fluorination technique, are reported for minerals from anhydrous and hydrous (i.e., amphibole-bearing) spinel lherzolites from Yemen, as well as from hydrous spinel lherzolites and amphibole megacrysts from Nunivak Island, Alaska. Oxygen isotopic compositions of olivine vary from 5.1-5.4%c and of pyroxene from 5.5-6.0%c and no systematic difference exists between minerals in hydrous and anhydrous lherzolites. The oxygen isotopic composition of the amphibole in the peridotites and of the amphibole megacrysts is also very homogeneous and varies from δ 18O = 5.3-5.6%o. These results indicate that the metasomatic minerals in the lherzolites are in oxygen isotopic equilibrium with the peridotitic minerals. The only isotopic disequilibria are observed in minerals which have grown in melt-pockets formed by partial melting of amphibole. The homogeneity of the oxygen isotopic ratios of mantle minerals in this study indicate that the fluids circulating in the mantle and precipitating amphibole or mica had the same oxygen isotopic compositions as the mantle protolith or that the fluids had been buffered by the isotopic composition of the olivine, the most abundant mineral, during percolation through the peridotites.

  15. Isotopic Composition of Barium in Single Presolar Silicon Carbide Grains

    NASA Technical Reports Server (NTRS)

    Savina, M. R.; Tripa, C. E.; Pellin, M. J.; Davis, A. M.; Clayton, R. N.; Lewis, R. S.; Amari, S.

    2002-01-01

    We have measured Ba isotope distributions in individual presolar SiC grains. We find that the Ba isotopic composition in mainstream SiC grains is consistent with models of nucleosynthesis in low to intermediate mass asymptotic giant branch (AGB) stars. Additional information is contained in the original extended abstract.

  16. Ruthenium Isotopic Composition of Terrestrial Materials, Iron Meteorites and Chondrites

    NASA Technical Reports Server (NTRS)

    Becker, H.; Walker, R. J.

    2002-01-01

    Ru isotopic compositions of magmatic iron meteorites and chondrites overlap with terrestrial Ru at the 0.3 to 0.9 (epsilon) level. Additional information is contained in the original extended abstract.

  17. Isotopic composition of atmospheric moisture from pan water evaporation measurements.

    PubMed

    Devi, Pooja; Jain, Ashok Kumar; Rao, M Someshwer; Kumar, Bhishm

    2015-01-01

    A continuous and reliable time series data of the stable isotopic composition of atmospheric moisture is an important requirement for the wider applicability of isotope mass balance methods in atmospheric and water balance studies. This requires routine sampling of atmospheric moisture by an appropriate technique and analysis of moisture for its isotopic composition. We have, therefore, used a much simpler method based on an isotope mass balance approach to derive the isotopic composition of atmospheric moisture using a class-A drying evaporation pan. We have carried out the study by collecting water samples from a class-A drying evaporation pan and also by collecting atmospheric moisture using the cryogenic trap method at the National Institute of Hydrology, Roorkee, India, during a pre-monsoon period. We compared the isotopic composition of atmospheric moisture obtained by using the class-A drying evaporation pan method with the cryogenic trap method. The results obtained from the evaporation pan water compare well with the cryogenic based method. Thus, the study establishes a cost-effective means of maintaining time series data of the isotopic composition of atmospheric moisture at meteorological observatories. The conclusions drawn in the present study are based on experiments conducted at Roorkee, India, and may be examined at other regions for its general applicability. PMID:26332982

  18. Isotope composition of carbon in amino acids of solid bitumens

    NASA Astrophysics Data System (ADS)

    Shanina, S. N.; Bushnev, D. A.

    2014-06-01

    Primary data are presented on the isotope composition of carbon in individual amino acids from solid bitumens and several biological objects. The amino acids of biological objects are characterized by wide variations of the isotope composition of carbon. This fact occurs owing to the difference in biochemical paths of metabolism resulting in the synthesis of individual amino acids. The δ13C values are somewhat decreased for individual amino acids in asphaltenes, varying from -7.7 to -31.7‰. The carbon of amino acids is weighted in kerits from Bad'el' compared to asphaltenes. All the natural bitumens retain the characteristic trend for natural substances: the isotopically heavy and light amino acids by carbon are glycine and leucine, respectively. The isotope composition of amino-acid carbon is lightened compared to natural bitumens in the samples formed under a pronounced thermal impact (asphalt-like crust and kirishite).

  19. The Palladium Isotopic Composition in Iron Meteorites

    NASA Technical Reports Server (NTRS)

    Chen, J. H.; Papanastassiou, D. A.

    2005-01-01

    Ru, Mo and Pd are very useful indicators for the identification of nucleosynthetic components. We have developed techniques for Pd isotopes, in an effort to check the extent of isotopic effects in this mass region and for a Pt-group element which is less refractory than Ru. Stable Pd isotopes are produced by the process only (102Pd), the s-process only (104Pd), the process only (Pd-110) and by both the r- and s-processes (Pd-105, Pd-106, Pd-108). Kelly and Wasserburg reported a hint of a shift in 102Pd (approx. 25(epsilon)u; 1(epsilon)u (triple bonds) 0.01%) in Santa Clara. Earlier searches for Mo and Ru isotopic anomalies were either positive or negative.

  20. Magnesium isotopic compositions of the Mesoproterozoic dolostones: Implications for Mg isotopic systematics of marine carbonates

    NASA Astrophysics Data System (ADS)

    Huang, Kang-Jun; Shen, Bing; Lang, Xian-Guo; Tang, Wen-Bo; Peng, Yang; Ke, Shan; Kaufman, Alan J.; Ma, Hao-Ran; Li, Fang-Bing

    2015-09-01

    Available Mg isotope data indicate that dolostones of different ages have overlapping range of Mg isotopic composition (δ26Mg) and there is no systematic difference among different types of dolomites. To further explore the Mg isotopic systematics of dolomite formation, we measured Mg isotopic compositions of Mesoproterozoic dolostones from the Wumishan Formation in North China Block, because dolomite formation in Mesoproterozoic might have been fundamentally different from the younger counterparts. Based on petrographic observations, three texturally-different dolomite phases (dolomicrite, subhedral dolomite and anhedral dolomite) are recognized in the Wumishan dolostones. Nevertheless, these three types of dolomites have similar δ26Mg values, ranging from -1.35‰ to -1.72‰, which are indistinguishable from Neoproterozoic and Phanerozoic dolostones. To explain δ26Mg values of dolostones, we simulate the Mg isotopic system during dolomite formation by applying the one-dimensional Diffusion-Advection-Reaction (1D-DAR) model, assuming that the contemporaneous seawater is the Mg source of dolostone. The 1D-DAR modeling results indicate that the degree of dolomitization is controlled by sedimentation rate, seawater Mg concentration, temperature, and reaction rate of dolomite formation, whereas Mg isotopic composition of dolostone is not only dependent on these factors, but also affected by δ26Mg of seawater and isotope fractionation during dolomite formation. Moreover, the 1D-DAR model predicts that dolomite formation within sediments has limited range of variation in δ26Mg with respect to limestones. Furthermore, the modeling results demonstrate that dolostone is always isotopically heavier than Ca-carbonate precipitated from seawater, explaining the systematic isotopic difference between dolostones and limestones. Finally, we can infer from the 1D-DAR model that early-formed dolostone at shallower depth of sediments is always isotopically lighter than that

  1. The 238U/235U isotope ratio of the Earth and the solar system: Constrains from a gravimetrically calibrated U double spike and implications for absolute Pb-Pb ages

    NASA Astrophysics Data System (ADS)

    Weyer, Stefan; Noordmann, Janine; Brennecka, Greg; Richter, Stephan

    2010-05-01

    The ratio of 238U and 235U, the two primordial U isotopes, has been assumed to be constant on Earth and in the solar system. The commonly accepted value for the 238U/235U ratio, which has been used in Pb-Pb dating for the last ~ 30 years, was 137.88. Within the last few years, it has been shown that 1) there are considerable U isotope variations (~1.3‰) within terrestrial material produced by isotope fractionation during chemical reactions [1-3] and 2) there are even larger isotope variations (at least 3.5‰) in calcium-aluminum-rich inclusions (CAIs) in meoteorites that define the currently accepted age of the solar system [4]. These findings are dramatic for geochronology, as a known 238U/235U is a requirement for Pb-Pb dating, the most precise dating technique for absolute ages. As 238U/235U variations can greatly affect the reported absolute Pb-Pb age, understanding and accurately measuring variation of the 238U/235U ratio in various materials is critical, With these new findings, the questions also arises of "How well do we know the average U isotope composition of the Earth and the solar system?" and "How accurate can absolute Pb-Pb ages be?" Our results using a gravimetrically calibrated 233U/236U double spike IRMM 3636 [5] indicate that the U standard NBL 950a, which was commonly used to define the excepted "natural" 238U/235U isotope ratio, has a slightly lower 238U/235U of 137.836 ± 0.024. This value is indistinguishable from the U isotope compositions for NBL 960 and NBL112A, which have been determined by several laboratories, also using the newly calibrated U double spike IRMM 3636 [6]. These findings provide new implications about the average U isotope composition of the Earth and the solar system. Basalts display a very tight range of U isotope variations (~0.25-0.32‰ relative to SRM 950a). Their U isotope composition is also very similar to that of chondrites [4], which however appear to show a slightly larger spread. Accepting terrestrial

  2. What does the oxygen isotope composition of rodent teeth record?

    NASA Astrophysics Data System (ADS)

    Royer, Aurélien; Lécuyer, Christophe; Montuire, Sophie; Amiot, Romain; Legendre, Serge; Cuenca-Bescós, Gloria; Jeannet, Marcel; Martineau, François

    2013-01-01

    Oxygen isotope compositions of tooth phosphate (δ18Op) were measured in 107 samples defined on the basis of teeth obtained from 375 specimens of extant rodents. These rodents were sampled from pellets collected in Europe from 38°N (Portugal) to 65°N (Finland) with most samples coming from sites located in France and Spain. Large oxygen isotopic variability in δ18Op is observed both at the intra- and inter-species scale within pellets from a given location. This isotopic variability is partly explained by heterochrony in tooth formation related to the short time of mineralization for all rodent species as well as the duration of mineralization that is species-dependent. Consequently, tooth phosphate of rodents records a short seasonal interval in the oxygen isotope compositions of meteoric waters (δ18Omw). In addition, inter-species isotopic variability observed in the same pellets suggests behavioural differences implying distinct isotopic compositions for species living in the same location. At the scale of Europe, a robust linear oxygen isotope fractionation equation was determined for Muroidea between the midrange δ18Op values and δ18Omw values: δ18Op=1.21(±0.20)δ18Omw+24.76(±2.70) with R2=0.79 (n=9; p<0.0001).

  3. Isotope pattern deconvolution for peptide mass spectrometry by non-negative least squares/least absolute deviation template matching

    PubMed Central

    2012-01-01

    Background The robust identification of isotope patterns originating from peptides being analyzed through mass spectrometry (MS) is often significantly hampered by noise artifacts and the interference of overlapping patterns arising e.g. from post-translational modifications. As the classification of the recorded data points into either ‘noise’ or ‘signal’ lies at the very root of essentially every proteomic application, the quality of the automated processing of mass spectra can significantly influence the way the data might be interpreted within a given biological context. Results We propose non-negative least squares/non-negative least absolute deviation regression to fit a raw spectrum by templates imitating isotope patterns. In a carefully designed validation scheme, we show that the method exhibits excellent performance in pattern picking. It is demonstrated that the method is able to disentangle complicated overlaps of patterns. Conclusions We find that regularization is not necessary to prevent overfitting and that thresholding is an effective and user-friendly way to perform feature selection. The proposed method avoids problems inherent in regularization-based approaches, comes with a set of well-interpretable parameters whose default configuration is shown to generalize well without the need for fine-tuning, and is applicable to spectra of different platforms. The R package IPPD implements the method and is available from the Bioconductor platform (http://bioconductor.fhcrc.org/help/bioc-views/devel/bioc/html/IPPD.html). PMID:23137144

  4. Calcium isotopic compositions of mid-ocean ridge basalts

    NASA Astrophysics Data System (ADS)

    Zhu, H.; Zhang, Z.; Sun, W.; Wang, G. Q.

    2015-12-01

    Previous studies have demonstrated that Earth's mantle has heterogeneous calcium isotopic compositions. But the reason why mantle has its heterogeneity remains uncertain. In general, δ44/40Ca values of mantle xenolith samples have a variation of >0.45‰. While ultramafic rocks, especially dunites, have higher δ44/40Ca values than volcanic rocks, and there is a positive correlation between δ44/40Ca and Ca/Mg. These phenomena imply that the heterogeneity of Ca isotopic compositions of mantle xenolith samples might result from different degrees of melt extraction, as indicated by large Ca isotopic fractionation between co-existing clinopyroxene and orthopyroxene. However, because ancient marine carbonate has its own unique calcium isotopic characteristics, recycling of even a small amount of ancient marine carbonates into the mantle could also cause the heterogeneity of Ca isotopes in Earth's mantle. This could be the reason why oceanic island basalts (OIB) have lighter Ca isotopic compositions than the mantle xenolith. Thus, the lighter Ca isotopic compositions in the mantle source cannot only be ascribed to magmatic processes. Therefore, it is more important to know calcium isotopic characteristics during partial melting and oceanic crust contamination.Mid-ocean ridge basalts (MORB) are formed from the partial melts of the upper mantle and are rarely affected by crustal contamination. Different types of MORB, including D-MORB, N-MORB and E-MORB, have experienced different degrees of partial melting and contamination of enriched end-members. Here we report calcium isotopic characteristic of different types of MORB, we believe it will be very helpful to understand the behaviors of Ca isotopes during partial melting and it is possible to provide further information to discover the reason why calcium isotopic compositions is heterogeneous in Earth's mantle. This work was supported by Natural Science Foundation of China (No. 41373007, No. 41490632 and No. 91328204

  5. Monitoring the water vapor isotopic composition in the North Atlantic

    NASA Astrophysics Data System (ADS)

    Sveinbjornsdottir, A. E.; Steen-Larsen, H.; Jonsson, T.; Johnsen, S. J.

    2011-12-01

    Water stable isotopes have during many decades been used as climate proxies and indicators for variations in the hydrological cycle. However we are to a great extent still using simple empirical relationships without any deeper theoretical understanding. In order to properly relate changes in the climate and hydrological cycle to changes in the observed stable water isotopic signal we must understand the underlying physical processes. Furthermore it is a challenge for General Climate Models to adequately represent the isotopes in the hydrological cycle because of lack of in-situ measurements of the atmospheric water-vapor composition in the source regions. During the fall of 2010 we installed an autonomous water vapor spectroscopy laser (from Los Gatos Research) in a lighthouse on the South Coast of Iceland (63.83 N 21.47W) with the plan to be operational for several years. The purpose of this installation was through monitoring of the water vapor isotopic composition to understand the physical processes governing the isotopic composition of the water vapor evaporated from the ocean as well as the processes of mixing between the free troposphere and marine boundary layer. Because of the remoteness of the monitoring site and simple topography we are able to isolate the 'fingerprint' on the isotopic signal in the water vapor from respectively the ocean and the interior highland leading to a near perfect case-study area. Using back-trajectories we find a strong influence of the origin of the air masses on the measured isotopic composition. The mixing of the marine-boundary layer is found to strongly influence the measured isotopic composition. The second order isotopic parameter, d-excess, is found to depend on both the isotopic composition as well as the relative humidity as prescribed by theories for evaporation from an ocean. The site likely represents a major source region for the moisture that later falls as snow on parts of the Greenland Ice Sheet. This leads to

  6. Isotopic compositions of cometary matter returned by Stardust.

    PubMed

    McKeegan, Kevin D; Aléon, Jerome; Bradley, John; Brownlee, Donald; Busemann, Henner; Butterworth, Anna; Chaussidon, Marc; Fallon, Stewart; Floss, Christine; Gilmour, Jamie; Gounelle, Matthieu; Graham, Giles; Guan, Yunbin; Heck, Philipp R; Hoppe, Peter; Hutcheon, Ian D; Huth, Joachim; Ishii, Hope; Ito, Motoo; Jacobsen, Stein B; Kearsley, Anton; Leshin, Laurie A; Liu, Ming-Chang; Lyon, Ian; Marhas, Kuljeet; Marty, Bernard; Matrajt, Graciela; Meibom, Anders; Messenger, Scott; Mostefaoui, Smail; Mukhopadhyay, Sujoy; Nakamura-Messenger, Keiko; Nittler, Larry; Palma, Russ; Pepin, Robert O; Papanastassiou, Dimitri A; Robert, François; Schlutter, Dennis; Snead, Christopher J; Stadermann, Frank J; Stroud, Rhonda; Tsou, Peter; Westphal, Andrew; Young, Edward D; Ziegler, Karen; Zimmermann, Laurent; Zinner, Ernst

    2006-12-15

    Hydrogen, carbon, nitrogen, and oxygen isotopic compositions are heterogeneous among comet 81P/Wild 2 particle fragments; however, extreme isotopic anomalies are rare, indicating that the comet is not a pristine aggregate of presolar materials. Nonterrestrial nitrogen and neon isotope ratios suggest that indigenous organic matter and highly volatile materials were successfully collected. Except for a single (17)O-enriched circumstellar stardust grain, silicate and oxide minerals have oxygen isotopic compositions consistent with solar system origin. One refractory grain is (16)O-enriched, like refractory inclusions in meteorites, suggesting that Wild 2 contains material formed at high temperature in the inner solar system and transported to the Kuiper belt before comet accretion. PMID:17170292

  7. Absolute Quantitation of Glycosylation Site Occupancy Using Isotopically Labeled Standards and LC-MS

    NASA Astrophysics Data System (ADS)

    Zhu, Zhikai; Go, Eden P.; Desaire, Heather

    2014-06-01

    N-linked glycans are required to maintain appropriate biological functions on proteins. Underglycosylation leads to many diseases in plants and animals; therefore, characterizing the extent of glycosylation on proteins is an important step in understanding, diagnosing, and treating diseases. To determine the glycosylation site occupancy, protein N-glycosidase F (PNGase F) is typically used to detach the glycan from the protein, during which the formerly glycosylated asparagine undergoes deamidation to become an aspartic acid. By comparing the abundance of the resulting peptide containing aspartic acid against the one containing non-glycosylated asparagine, the glycosylation site occupancy can be evaluated. However, this approach can give inaccurate results when spontaneous chemical deamidation of the non-glycosylated asparagine occurs. To overcome this limitation, we developed a new method to measure the glycosylation site occupancy that does not rely on converting glycosylated peptides to their deglycosylated forms. Specifically, the overall protein concentration and the non-glycosylated portion of the protein are quantified simultaneously by using heavy isotope-labeled internal standards coupled with LC-MS analysis, and the extent of site occupancy is accurately determined. The efficacy of the method was demonstrated by quantifying the occupancy of a glycosylation site on bovine fetuin. The developed method is the first work that measures the glycosylation site occupancy without using PNGase F, and it can be done in parallel with glycopeptide analysis because the glycan remains intact throughout the workflow.

  8. Determination of plutonium isotopic composition by gamma-ray spectroscopy

    SciTech Connect

    Sampson, T.E.; Hsue, S.T.; Parker, J.L.; Johnson, S.S.; Bowersox, D.F.

    1981-01-01

    We discuss the general approach, computerized data analysis methods, and results of measurements used to determine the isotopic composition of plutonium by gamma-ray spectroscopy. The simple techniques are designed to be applicable to samples of arbitrary size, geometry, age, chemical, and isotopic composition. The combination of the gamma spectroscopic measurement of isotopic composition coupled with calorimetric measurement of total sample power is shown to give a totally nondestructive determination of sample plutonium mass with a precision of 0.6% for 1000-g samples of PuO/sub 2/ with 12% /sup 240/Pu content. The precision of isotopic measurements depends upon many factors, including sample size, sample geometry, and isotopic content. Typical ranges are found to be /sup 238/Pu, 1 to 10%; /sup 239/Pu, 0.1 to 0.5%; /sup 240/Pu, 2 to 5%; /sup 241/Pu, 0.3 to 0.7%; /sup 242/Pu (determined by isotopic correlation); and /sup 241/Am, 0.2 to 10%.

  9. Zinc isotope fractionation during magmatic differentiation and the isotopic composition of the bulk Earth

    USGS Publications Warehouse

    Chen, Heng; Savage, Paul S.; Teng, Fang-Zehn; Helz, Rosalind T.; Moynier, Frédéric

    2013-01-01

    he zinc stable isotope system has been successfully applied to many and varied fields in geochemistry, but to date it is still not completely clear how this isotope system is affected by igneous processes. In order to evaluate the potential application of Zn isotopes as a proxy for planetary differentiation and volatile history, it is important to constrain the magnitude of Zn isotopic fractionation induced by magmatic differentiation. In this study we present high-precision Zn isotope analyses of two sets of chemically diverse, cogenetic samples from Kilauea Iki lava lake, Hawaii, and Hekla volcano, Iceland, which both show clear evidence of having undergone variable and significant degrees of magmatic differentiation. The Kilauea Iki samples display small but resolvable variations in Zn isotope composition (0.26‰66Zn66Zn defined as the per mille deviation of a sample's 66Zn/64Zn compositional ratio from the JMC-Lyon standard), with the most differentiated lithologies exhibiting more positive δ66Zn values. This fractionation is likely a result of the crystallization of olivine and/or Fe–Ti oxides, which can both host Zn in their crystal structures. Samples from Hekla have a similar range of isotopic variation (0.22‰66Zn66Zn=0.28±0.05‰ (2s.d.).

  10. Zinc isotope fractionation during magmatic differentiation and the isotopic composition of the bulk Earth

    NASA Astrophysics Data System (ADS)

    Chen, Heng; Savage, Paul S.; Teng, Fang-Zhen; Helz, Rosalind T.; Moynier, Frédéric

    2013-05-01

    The zinc stable isotope system has been successfully applied to many and varied fields in geochemistry, but to date it is still not completely clear how this isotope system is affected by igneous processes. In order to evaluate the potential application of Zn isotopes as a proxy for planetary differentiation and volatile history, it is important to constrain the magnitude of Zn isotopic fractionation induced by magmatic differentiation. In this study we present high-precision Zn isotope analyses of two sets of chemically diverse, cogenetic samples from Kilauea Iki lava lake, Hawaii, and Hekla volcano, Iceland, which both show clear evidence of having undergone variable and significant degrees of magmatic differentiation. The Kilauea Iki samples display small but resolvable variations in Zn isotope composition (0.26‰<δ66Zn<0.36‰; δ66Zn defined as the per mille deviation of a sample's 66Zn/64Zn compositional ratio from the JMC-Lyon standard), with the most differentiated lithologies exhibiting more positive δ66Zn values. This fractionation is likely a result of the crystallization of olivine and/or Fe-Ti oxides, which can both host Zn in their crystal structures. Samples from Hekla have a similar range of isotopic variation (0.22‰<δ66Zn<0.33‰), however, the degree of fractionation caused by magmatic differentiation is less significant (only 0.07‰) and no correlation between isotope composition and degree of differentiation is seen. We conclude that high temperature magmatic differentiation can cause Zn isotope fractionation that is resolvable at current levels of precision, but only in compositionally-evolved lithologies. With regards to primitive (ultramafic and basaltic) material, this signifies that the terrestrial mantle is essentially homogeneous with respect to Zn isotopes. Utilizing basaltic and ultramafic sample analyses, from different geologic settings, we estimate that the average Zn isotopic composition of Bulk Silicate Earth is δ66Zn=0.28

  11. Anomalous isotopic composition of cosmic rays

    SciTech Connect

    Woosley, S.E.; Weaver, T.A.

    1980-06-20

    Recent measurements of nonsolar isotopic patterns for the elements neon and (perhaps) magnesium in cosmic rays are interpreted within current models of stellar nucleosynthesis. One possible explanation is that the stars currently responsible for cosmic-ray synthesis in the Galaxy are typically super-metal-rich by a factor of two to three. Other possibilities include the selective acceleration of certain zones or masses of supernovas or the enhancement of /sup 22/Ne in the interstellar medium by mass loss from red giant stars and planetary nebulas. Measurements of critical isotopic ratios are suggested to aid in distinguishing among the various possibilities. Some of these explanations place significant constraints on the fraction of cosmic ray nuclei that must be fresh supernova debris and the masses of the supernovas involved. 1 figure, 3 tables.

  12. Chemical and isotopic compositions in acid residues from various meteorites

    NASA Technical Reports Server (NTRS)

    Kano, N.; Yamakoshi, K.; Matsuzaki, H.; Nogami, K.

    1993-01-01

    We are planning to carry out systematic isotopic investigations of Ru, Mg, etc., in primordial samples. The investigations will be pursued in the context of a study of the pre-history of the solar system. It is hoped that the study will yield direct evidence for processes of nucleosynthesis in the pre-solar stage and detection of extinct radioactive nuclides. In this paper, we present the results of chemical compositions of acid residues obtained from three types of meteorites: Canyon Diablo (IA), Allende (CV3), and Nuevo Mercuro (H5); and the preliminary results of Ru isotopic compositions.

  13. Cd Isotopic Composition Measured by Plasma Source Mass Spectrometry on Natural and Anthropogenic Materials. A Preliminary Outline of Cd Isotope Systematics

    NASA Astrophysics Data System (ADS)

    Innocent, C.

    2004-05-01

    Cadmium is a trace metal that is used as a geochemical tracer of natural processes, like biological productivity and paleoproductivity, and also of anthropogenic pollution, as Cd is known to be a toxic heavy metal that has become a major environmental and health concern. For these purposes, an outstanding issue is to determine whether Cd, like a number of metallic elements (e.g. Fe, Cu, Zn, Mo, Tl), may display variable isotopic compositions in natural and/or industrial compounds. It is known that Cd may display variable isotopic composition. Indeed, isotopic fractionation processes have been documented in some meteorites and in lunar soils. Consequently, due to its relatively low boiling point (767\\deg C) and also to the large mass range covered by its isotopes (10 mass units), Cd might fractionate isotopically, for example during the outpouring of acidic volcanic magmas and/or the emplacement of granitoids. On another hand, isotopic fractionation could also occur during human activities like refuse incineration or industrial manufacturing, for instance. Finally, biologically-induced isotopic fractionation should not be ruled out, as it is clearly evidenced for other metals, like Fe. A high precision method has been developed for determining the isotopic composition of Cd by plasma source mass spectrometry (Neptune). This method holds on the standard-bracketing technique, owing to the availability of Cd solutions of known isotopic composition provided by the University of M\\H{u}nster. This allows to correct precisely for mass fractionation that occurs in the plasma source mass spectrometer. It is also critical for the analysis to be possible to work with Cd solutions of very high purity. Chemical isolation of Cd involves 3 steps, and may be also suitable for Cd isotopic measurements using solid source mass spectrometry. Preliminary results suggest that Cd is likely to fractionate during smelting activities, as indicated by measurements on mining waste. The

  14. Carbon isotopic composition of individual Precambrian microfossils

    NASA Astrophysics Data System (ADS)

    House, Christopher H.; Schopf, J. William; McKeegan, Kevin D.; Coath, Christopher D.; Harrison, T. Mark; Stetter, Karl O.

    2000-08-01

    Ion microprobe measurements of carbon isotope ratios were made in 30 specimens representing six fossil genera of microorganisms petrified in stromatolitic chert from the ˜850 Ma Bitter Springs Formation, Australia, and the ˜2100 Ma Gunflint Formation, Canada. The δ13CPDB values from individual microfossils of the Bitter Springs Formation ranged from -21.3 ± 1.7‰ to -31.9 ± 1.2‰, and the δ13CPDB values from microfossils of the Gunflint Formation ranged from -32.4 ± 0.7‰ to -45.4 ± 1.2‰. With the exception of two highly 13C-depleted Gunflint microfossils, the results generally yield values consistent with carbon fixation via either the Calvin cycle or the acetyl-CoA pathway. However, the isotopic results are not consistent with the degree of fractionation expected from either the 3-hydroxypropionate cycle or the reductive tricarboxylic acid cycle, suggesting that the microfossils studied did not use either of these pathways for carbon fixation. The morphologies of the microfossils suggest an affinity to the cyanobacteria, and our carbon isotopic data are consistent with this assignment.

  15. Stable isotopic compositions in Australian precipitation

    NASA Astrophysics Data System (ADS)

    Liu, Jianrong; Fu, Guobin; Song, Xianfang; Charles, Stephen P.; Zhang, Yinghua; Han, Dongmei; Wang, Shiqin

    2010-12-01

    Stable deuterium (δD) and oxygen-18 (δ18O) isotopes in 1962 to 2002 precipitation from the seven Australian stations of the Global Network of Isotopes in Precipitation (GNIP) were used to investigate isotope characteristics including temporal and spatial distributions across different regions of Australia. On the basis of 1534 samples, the local meteoric water line (LMWL) was established as δD = 7.10δ18O + 8.21. δ18O showed a depletion trend from north and south to central Australia (a continental effect) and from west to east. Precipitation amount effects were generally greater than temperature effects, with quadratic or logarithmic correlations describing δ/T and δ/P better than linear relationships. Nonlinear stepwise regression was used to determine the significant meteorological control factors for each station, explaining about 50% or more of the δ18O variations. Geographical control factors for δ18O were given by the relationship δ18O (‰) = -0.005 longitude (°) - 0.034 latitude (°)-0.003 altitude (m) - 4.753. Four different types of d-excess patterns demonstrated particular precipitation formation conditions for four major seasonal rainfall zones. Finally, wavelet coherence (WTC) between δ18O and SOI confirmed that the influence of ENSO decreased from east and north to west Australia.

  16. Carbon isotopic composition of individual Precambrian microfossils

    NASA Technical Reports Server (NTRS)

    House, C. H.; Schopf, J. W.; McKeegan, K. D.; Coath, C. D.; Harrison, T. M.; Stetter, K. O.

    2000-01-01

    Ion microprobe measurements of carbon isotope ratios were made in 30 specimens representing six fossil genera of microorganisms petrified in stromatolitic chert from the approximately 850 Ma Bitter Springs Formation, Australia, and the approximately 2100 Ma Gunflint Formation, Canada. The delta 13C(PDB) values from individual microfossils of the Bitter Springs Formation ranged from -21.3 +/- 1.7% to -31.9 +/- 1.2% and the delta 13C(PDB) values from microfossils of the Gunflint Formation ranged from -32.4 +/- 0.7% to -45.4 +/- 1.2%. With the exception of two highly 13C-depleted Gunflint microfossils, the results generally yield values consistent with carbon fixation via either the Calvin cycle or the acetyl-CoA pathway. However, the isotopic results are not consistent with the degree of fractionation expected from either the 3-hydroxypropionate cycle or the reductive tricarboxylic acid cycle, suggesting that the microfossils studied did not use either of these pathways for carbon fixation. The morphologies of the microfossils suggest an affinity to the cyanobacteria, and our carbon isotopic data are consistent with this assignment.

  17. Mercury isotope compositions in North American forest soils and litters

    NASA Astrophysics Data System (ADS)

    Zheng, W.; Obrist, D.; Bergquist, B. A.

    2013-12-01

    Soils represent one of the largest reservoirs of mercury on Earth, playing a critical role in the natural cycle of mercury by acting as both a sink and source. However, it is not well understood how soils sequestrate and remobilize Hg. Natural variations in stable Hg isotopes are being explored as a promising tool in studying the transformation and transport of Hg. However, Hg isotopic data in soils is scarce. In addition, the limited isotopic data that exists is significantly different from those of atmospheric Hg, which is one of the major sources of Hg to soils. For example, Hg mass independent fractionation (MIF, typically reported as Δ199Hg) is positive in atmospheric wet deposition, but most soils display negative Δ199Hg. MIF on 200Hg (Δ200Hg) is also observed in atmospheric wet deposition, but not in soils. The discrepancy between soils and atmospheric samples is still unexplained. In this study, we surveyed the Hg isotope compositions in soil profiles, litters and fresh vegetation from four different forest sites across United States (Thompson forest, WA, Truckee, CA, Niwot Ridge, CO and Howland, MA). The current results from the WA site show that soils primarily display negative mass dependent fractionation for the even isotopes (MDF, reported as δ202Hg) with values for δ202Hg of up to -2.0‰. Significant MIF for both odd isotopes is also observed in all WA soil samples and Δ199Hg is mostly negative (up to -0.4‰). No MIF on 200Hg is observed in these soils. The negative Δ199Hg in soils is inconsistent with the positive Δ199Hg reported in atmospheric wet deposition, suggesting that either Hg transformations within or on the surface of soils and/or plants alter its isotope composition after deposition or other types of Hg deposition (e.g., Hg(0) or Hg(II) dry deposition) is more predominant. The Δ199Hg/Δ201Hg ratio is close to 1 in the soils, which is consistent with the results of laboratory photochemical reduction of inorganic Hg

  18. The Stable Isotopic Composition of Atmospheric CO2

    NASA Astrophysics Data System (ADS)

    Yakir, D.

    2003-12-01

    When a bean leaf was sealed in a closed chamber under a lamp (Rooney, 1988), in two hours the atmospheric CO2 in the microcosm reached an isotopic steady state with a 13C abundance astonishingly similar to the global mean value of atmospheric CO2 at that time (-7.5‰ in the δ13C notation introduced below). Almost concurrently, another research group sealed a suspension of asparagus cells in a different type of microcosm in which within about two hours the atmospheric O2 reached an isotopic steady state with 18O enrichment relative to water in the microcosm that was, too, remarkably similar to the global-scale offset between atmospheric O2 and mean ocean water (21‰ versus 23.5‰ in the δ18O notation introduced below; Guy et al., 1987). These classic experiments capture some of the foundations underlying the isotopic composition of atmospheric CO2 and O2. First, in both cases the biological system rapidly imposed a unique isotopic value on the microcosms' atmosphere via their massive photosynthetic and respiratory exchange of CO2 and O2. Second, in both cases the biological system acted on materials with isotopic signals previously formed by the global carbon and hydrological cycles. That is, the bean leaf introduced its previously formed organic matter (the source of the CO2 respired into microcosm's atmosphere), and the asparagus cells were introduced complete with local tap water (from which photosynthesis released molecular oxygen). Therefore, while the isotopic composition of the biological system used was slave to long-term processes, intense metabolic processes centered on few specific enzymes (Yakir, 2002) dictated the short-term atmospheric composition.In a similar vein, on geological timescales of millions of years, the atmosphere and its isotopic composition are integral parts of essentially a single dynamic ocean-atmosphere-biosphere system. This dynamic system exchanges material, such as carbon and oxygen, with the sediments and the lithosphere via

  19. The Clumped Isotope Composition of Biogenic Methane.

    NASA Astrophysics Data System (ADS)

    Sessions, A. L.; Douglas, P. M.; Eiler, J. M.; Stolper, D. A.

    2015-12-01

    The excess or lack of 13CH3D, a doubly substituted ("clumped") isotopologue of methane, relative to that expected for a random distribution of isotopes across molecules, is a function of the processes that generated the methane. For high-temperature thermogenic methane, which typically achieves internal equilibrium, an excess of 13CH3D is expected and the amount of excess can serve as a thermometer. In contrast, biogenic methane often - though not always - has a smaller excess of clumped isotopologues, and sometimes even a deficit of clumped species ("anti-clumped"). The effect presumably arises from kinetic isotope effects accompanying enzymatic reactions in the methanogenic pathway, though the particular reaction(s) has not yet been positively identified. The decrease in clumping is also known to correlate with both the reversibility of the pathway and the methane flux. In this talk, we will present recent data bearing on the origin and utility of biologic fractionations of clumped isotopologues in methane. Preliminary data suggest that methane deriving from the fermentative pathway is enriched in D-bearing isotopologues, at the same level of clumping, relative to that derived from the CO2-reductive pathway. This property offers another potential means to distinguish biogenic methane sources in the environment. Recently, we have also begun to measure the 12CH2D2 isotopologue, for which equilibrium and kinetic isotope effects are predicted to be distinct from 13CH3D. Preliminary data suggest that the combination of both doubly-substituted isotopologues will be especially useful for disentangling mixtures containing biogenic gas.

  20. H-Isotopic Composition of Apatite in Northwest Africa 7034

    NASA Technical Reports Server (NTRS)

    McCubbin, F. M.; Barnes, J. J.; Santos, A. R.; Boyce, J. W.; Anand, M.; Franchi, I. A.; Agee, C. B.

    2016-01-01

    Northwest Africa (NWA) 7034 and its pairings comprise a regolith breccia with a basaltic bulk composition [1] that yields a better match than any other martian meteorite to estimates of Mars' bulk crust composition [1]. Given the similarities between NWA 7034 and the martian crust, NWA 7034 may represent an important sample for constraining the crustal composition of components that cannot be measured directly by remote sensing. In the present study, we seek to constrain the H isotopic composition of the martian crust using Cl-rich apatite in NWA 7034.

  1. Measurement of Plutonium Isotopic Composition - MGA

    SciTech Connect

    Vo, Duc Ta

    2015-08-21

    In this module, we will use the Canberra InSpector-2000 Multichannel Analyzer with a high-purity germanium detector (HPGe) and the MGA isotopic anlysis software to assay a variety of plutonium samples. The module provides an understanding of the MGA method, its attributes and limitations. You will assess the system performance by measuring a range of materials similar to those you may assay in your work. During the final verification exercise, the results from MGA will be combined with the 240Pueff results from neutron coincidence or multiplicity counters so that measurements of the plutonium mass can be compared with the operator-declared (certified) values.

  2. Heavy nickel isotope compositions in rivers and the oceans

    NASA Astrophysics Data System (ADS)

    Cameron, V.; Vance, D.

    2014-03-01

    Nickel is a biologically-active trace metal whose dissolved concentration depth profiles in the ocean show nutrient-like behaviour. If the pronounced removal of nickel from the dissolved phase in the surface ocean, and its return in the deep, is associated with an isotopic fractionation nickel isotopes may be able to yield constraints on the precise biogeochemical processes involved. Here we present the first nickel isotope data for seawater along with data for the dissolved phase of rivers, one of the principal sources of nickel to the oceans. The dissolved phase of rivers exhibits substantial variability in both Ni concentration and δ60Ni: from 2.2 to 35 nmol kg-1 and +0.29 to +1.34‰, respectively. The most striking result from the nickel isotope analyses of rivers is that they are substantially heavier (by up to 1‰ for δ60Ni) than the range for silicate rocks on the continents, a finding that is analogous to that for other transition metal isotope systems. If the data presented here are close to representative of the global riverine flux, they suggest an annual input of Ni to the oceans of 3.6 × 108moles, and a discharge- and concentration-weighted δ60Ni average of +0.80‰. The relationship between Ni isotopes and concentrations shows similarities with those for other transition metal isotope systems, where the main control has been suggested to be isotopic partitioning between the dissolved phase and particulates, either in the weathering environment or during transport. In stark contrast to the rivers, the dataset for seawater is very homogeneous, with 2SD of the entire dataset being only twice the analytical reproducibility. The second main feature is that seawater is distinctly heavier in Ni isotopes than rivers. The average δ60Ni is 1.44 ± 0.15‰ (2SD), and only 2 of the 29 seawater analyses have a Ni isotopic composition that is lighter than the heaviest river. The lack of an isotopic shift associated with the drawdown of nickel concentrations

  3. What controls the isotopic composition of Greenland surface snow?

    NASA Astrophysics Data System (ADS)

    Steen-Larsen, H. C.; Masson-Delmotte, V.; Hirabayashi, M.; Winkler, R.; Satow, K.; Prié, F.; Bayou, N.; Brun, E.; Cuffey, K. M.; Dahl-Jensen, D.; Dumont, M.; Guillevic, M.; Kipfstuhl, J.; Landais, A.; Popp, T.; Risi, C.; Steffen, K.; Stenni, B.; Sveinbjörnsdottír, A.

    2013-10-01

    Water stable isotopes in Greenland ice core data provide key paleoclimatic information, and have been compared with precipitation isotopic composition simulated by isotopically-enabled atmospheric models. However, post-deposition processes linked with snow metamorphism remain poorly documented. For this purpose, a monitoring of the isotopic composition (δ18O, δD) of surface water vapor, precipitation and samples of top (0.5 cm) snow surface has been conducted during two summers (2011-2012) at NEEM, NW Greenland. The measurements also include a subset of 17O-excess measurements over 4 days, and the measurements span the 2012 Greenland heat wave. Our observations are consistent with calculations assuming isotopic equilibrium between surface snow and water vapor. We observe a strong correlation between surface vapor δ18O and air temperature (0.85 ± 0.11 ‰ °C-1 (R = 0.76) for 2012). The correlation with air temperature is not observed in precipitation data or surface snow data. Deuterium excess (d-excess) is strongly anti-correlated with δ18O with a stronger slope for vapor than for precipitation and snow surface data. During nine 1-5 days periods between precipitation events, our data demonstrate parallel changes of δ18O and d-excess in surface snow and surface vapor. The changes in δ18O of the vapor are similar or larger than those of the snow δ18O. It is estimated that 6 to 20% of the surface snow mass is exchanged with the atmosphere using the CROCUS snow model. In our data, the sign of surface snow isotopic changes is not related to the sign or magnitude of sublimation or condensation. Comparisons with atmospheric models show that day-to-day variations in surface vapor isotopic composition are driven by synoptic weather and changes in air mass trajectories and distillation histories. We suggest that, in-between precipitation events, changes in the surface snow isotopic composition are driven by these changes in surface vapor isotopic composition. This

  4. What controls the isotopic composition of Greenland surface snow?

    NASA Astrophysics Data System (ADS)

    Steen-Larsen, H. C.; Masson-Delmotte, V.; Hirabayashi, M.; Winkler, R.; Satow, K.; Prié, F.; Bayou, N.; Brun, E.; Cuffey, K. M.; Dahl-Jensen, D.; Dumont, M.; Guillevic, M.; Kipfstuhl, S.; Landais, A.; Popp, T.; Risi, C.; Steffen, K.; Stenni, B.; Sveinbjörnsdottír, A. E.

    2014-02-01

    Water stable isotopes in Greenland ice core data provide key paleoclimatic information, and have been compared with precipitation isotopic composition simulated by isotopically enabled atmospheric models. However, post-depositional processes linked with snow metamorphism remain poorly documented. For this purpose, monitoring of the isotopic composition (δ18O, δD) of near-surface water vapor, precipitation and samples of the top (0.5 cm) snow surface has been conducted during two summers (2011-2012) at NEEM, NW Greenland. The samples also include a subset of 17O-excess measurements over 4 days, and the measurements span the 2012 Greenland heat wave. Our observations are consistent with calculations assuming isotopic equilibrium between surface snow and water vapor. We observe a strong correlation between near-surface vapor δ18O and air temperature (0.85 ± 0.11‰ °C-1 (R = 0.76) for 2012). The correlation with air temperature is not observed in precipitation data or surface snow data. Deuterium excess (d-excess) is strongly anti-correlated with δ18O with a stronger slope for vapor than for precipitation and snow surface data. During nine 1-5-day periods between precipitation events, our data demonstrate parallel changes of δ18O and d-excess in surface snow and near-surface vapor. The changes in δ18O of the vapor are similar or larger than those of the snow δ18O. It is estimated using the CROCUS snow model that 6 to 20% of the surface snow mass is exchanged with the atmosphere. In our data, the sign of surface snow isotopic changes is not related to the sign or magnitude of sublimation or deposition. Comparisons with atmospheric models show that day-to-day variations in near-surface vapor isotopic composition are driven by synoptic variations and changes in air mass trajectories and distillation histories. We suggest that, in between precipitation events, changes in the surface snow isotopic composition are driven by these changes in near-surface vapor

  5. Oxygen isotopic constraints on the composition of the moon

    NASA Technical Reports Server (NTRS)

    Grossman, L.; Clayton, R. N.; Mayeda, T. K.

    1974-01-01

    The mean oxygen isotopic composition of 5 Apollo 17 soils, one Apollo 17 breccia and one Apollo 12 soil is delta O-18 = 5.63 + or - .05 and delta O-17 = 3.8 + or - .2%. These values are within several tenths of a part permil of the composition of a large fraction of the lunar interior. High-temperature condensate aggregates from Allende and other C2 and C3 chondrites are vastly enriched in O-16 compared to this composition. The moon cannot be a mixture of ordinary chondrites and Allende inclusions, nor can it be derived from such a mixture by chemical fractionation processes. The moon's isotopic composition is consistent with a mixture of high- and low-temperature condensates but the refractory fraction would have to be free of the O-16-rich component so prevalent in the meteoritic aggregates, a fact which makes such models less attractive than they once seemed.

  6. Pressure-dependent isotopic composition of iron alloys.

    PubMed

    Shahar, A; Schauble, E A; Caracas, R; Gleason, A E; Reagan, M M; Xiao, Y; Shu, J; Mao, W

    2016-04-29

    Our current understanding of Earth's core formation is limited by the fact that this profound event is far removed from us physically and temporally. The composition of the iron metal in the core was a result of the conditions of its formation, which has important implications for our planet's geochemical evolution and physical history. We present experimental and theoretical evidence for the effect of pressure on iron isotopic composition, which we found to vary according to the alloy tested (FeO, FeH(x), or Fe3C versus pure Fe). These results suggest that hydrogen or carbon is not the major light-element component in the core. The pressure dependence of iron isotopic composition provides an independent constraint on Earth's core composition. PMID:27126042

  7. Pressure-dependent isotopic composition of iron alloys

    NASA Astrophysics Data System (ADS)

    Shahar, A.; Schauble, E. A.; Caracas, R.; Gleason, A. E.; Reagan, M. M.; Xiao, Y.; Shu, J.; Mao, W.

    2016-04-01

    Our current understanding of Earth’s core formation is limited by the fact that this profound event is far removed from us physically and temporally. The composition of the iron metal in the core was a result of the conditions of its formation, which has important implications for our planet’s geochemical evolution and physical history. We present experimental and theoretical evidence for the effect of pressure on iron isotopic composition, which we found to vary according to the alloy tested (FeO, FeHx, or Fe3C versus pure Fe). These results suggest that hydrogen or carbon is not the major light-element component in the core. The pressure dependence of iron isotopic composition provides an independent constraint on Earth’s core composition.

  8. Fe Isotope Composition of Neoproterozoic Post-Glacial "Cap Dolostones"

    NASA Astrophysics Data System (ADS)

    Halverson, G. P.

    2005-12-01

    The largest variations in the Fe isotope composition in the geological record are found in sedimentary rocks, presumably as the result of redox transformations of iron during mineral precipitation, microbial processing, and diagenesis (Johnson et al., Cont. Min. Petrol., 2003). Systematic trends in the variability of the Fe isotope composition of sulfide minerals formed in ancient marine black shales broadly mirror patterns in sulfur isotope data (Δ33S, Δ34S), which are consistent with geological and other geochemical evidence for the progressive oxidation of the earth's surface during the Precambrian (Rouxel et al., Science, 2005). Therefore, the record of the Fe isotope composition of minerals formed in the marine environment appears to be a promising proxy for the redox evolution of the ocean. We have developed a method to extract the marine Fe isotope composition from carbonates in an attempt to establish higher resolution records of changes in marine redox changes than permitted by black shale geochemistry. We have applied this method to the study of ca. 635 Ma iron-rich dolostones, which are found in Neoproterozoic successions worldwide and immediately post-date a purported snowball (Marinoan) glaciation during which time the deep ocean is thought to have become anoxic (Hoffman et al., Science, 1998), allowing its Fe isotopic composition to evolve towards the composition of relatively light (δ57Fe vs. IRMM-14 ~ -0.6‰) hydrothermal iron (Beard et al., Geology, 2003). Fe isotope compositions were measured relative to IRMM-14 in medium-resolution mode on a Neptune MC-ICP-MS with a long-term external (2σ) reproducibility of < 0.04‰/amu. Preliminary data on dolomite samples from Svalbard, northern Namibia and northwest Canada show a range in δ57Fe values from -0.65 to 0.04‰, similar to the range found in siderite and Fe-rich dolomite in ancient BIFs (Johsnon et al., 2003) and to values for the Namibian cap dolostone reported by Leighton et al

  9. Isotopic composition of transpiration and rates of change in leaf water isotopologue storage in response to environmental variables.

    PubMed

    Simonin, Kevin A; Roddy, Adam B; Link, Percy; Apodaca, Randy; Tu, Kevin P; Hu, Jia; Dawson, Todd E; Barbour, Margaret M

    2013-12-01

    During daylight hours, the isotope composition of leaf water generally approximates steady-state leaf water isotope enrichment model predictions. However, until very recently there was little direct confirmation that isotopic steady-state (ISS) transpiration in fact exists. Using isotope ratio infrared spectroscopy (IRIS) and leaf gas exchange systems we evaluated the isotope composition of transpiration and the rate of change in leaf water isotopologue storage (isostorage) when leaves were exposed to variable environments. In doing so, we developed a method for controlling the absolute humidity entering the gas exchange cuvette for a wide range of concentrations without changing the isotope composition of water vapour. The measurement system allowed estimation of (18)O enrichment both at the evaporation site and for bulk leaf water, in the steady state and the non-steady state. We show that non-steady-state effects dominate the transpiration isoflux even when leaves are at physiological steady state. Our results suggest that a variable environment likely prevents ISS transpiration from being achieved and that this effect may be exacerbated by lengthy leaf water turnover times due to high leaf water contents. PMID:23647101

  10. Heavy nickel isotope compositions in rivers and the oceans

    NASA Astrophysics Data System (ADS)

    Cameron, V.; Vance, D.

    2014-03-01

    Nickel is a biologically-active trace metal whose dissolved concentration depth profiles in the ocean show nutrient-like behaviour. If the pronounced removal of nickel from the dissolved phase in the surface ocean, and its return in the deep, is associated with an isotopic fractionation nickel isotopes may be able to yield constraints on the precise biogeochemical processes involved. Here we present the first nickel isotope data for seawater along with data for the dissolved phase of rivers, one of the principal sources of nickel to the oceans. The dissolved phase of rivers exhibits substantial variability in both Ni concentration and δ60Ni: from 2.2 to 35 nmol kg-1 and +0.29 to +1.34‰, respectively. The most striking result from the nickel isotope analyses of rivers is that they are substantially heavier (by up to 1‰ for δ60Ni) than the range for silicate rocks on the continents, a finding that is analogous to that for other transition metal isotope systems. If the data presented here are close to representative of the global riverine flux, they suggest an annual input of Ni to the oceans of 3.6 × 108moles, and a discharge- and concentration-weighted δ60Ni average of +0.80‰. The relationship between Ni isotopes and concentrations shows similarities with those for other transition metal isotope systems, where the main control has been suggested to be isotopic partitioning between the dissolved phase and particulates, either in the weathering environment or during transport. In stark contrast to the rivers, the dataset for seawater is very homogeneous, with 2SD of the entire dataset being only twice the analytical reproducibility. The second main feature is that seawater is distinctly heavier in Ni isotopes than rivers. The average δ60Ni is 1.44 ± 0.15‰ (2SD), and only 2 of the 29 seawater analyses have a Ni isotopic composition that is lighter than the heaviest river. The lack of an isotopic shift associated with the drawdown of nickel concentrations

  11. A reconnaissance of the boron isotopic composition of tourmaline

    SciTech Connect

    Swihart, G.H.; Moore, P.B. )

    1989-04-01

    A preliminary investigation of the boron isotopic composition of tourmaline from some boron-rich associations has been made. The results for tourmaline from metasedimentary paragneisses (n = 12) range from {delta}{sup 11}B = {minus}22 to +22 per mil. These data mainly fall between the boron isotopic compositions of normal marine sediments with {delta}{sup 11}B = {minus}2 to +5 per mil and seawater with {delta}{sup 11}B = +39.5 per mil. Tourmaline samples from granitic pegmatites (n = 6), on the other hand, range from {delta}{sup 11}B = {minus}12 to {minus}5 per mil. The data provide a rudimentary indication of the range of boron isotopic variation in tourmaline, some of the processes leading to this range, and some possible geochemical tracer applications.

  12. Converting isotope ratios to diet composition - the use of mixing models - June 2010

    EPA Science Inventory

    One application of stable isotope analysis is to reconstruct diet composition based on isotopic mass balance. The isotopic value of a consumer’s tissue reflects the isotopic values of its food sources proportional to their dietary contributions. Isotopic mixing models are used ...

  13. Authentication of bell peppers using boron and strontium isotope compositions

    NASA Astrophysics Data System (ADS)

    Rosner, Martin; Pritzkow, Wolfgang; Vogl, Jochen; Voerkelius, Susanne

    2010-05-01

    The wrong declaration of food in terms of geographical origin and production method is a major problem for the individual consumer and public regulatory authorities. The authentication of food matrices using H-C-N-O-S isotopic compositions is already well established. However, specific questions require additional isotopic systems, which are more diagonstic for the source reservoires involved or production methods used. Here we present B and Sr isotopic compositions of bell peppers from Europe (Germany, Austria, Netherlands, Spain) and Israel to verfiy their origin. The bell peppers' B isotopic compositions between different locations are highly variable (d11BNISTSRM951 -8 to +35 ‰), whereas the 87Sr/86Sr ratios are all close to modern seawater Sr isotopic composition of about 0.7092 (0.7078 to 0.7107), but still can reliably be distinguished. Distinct isotopically heavy and light B isotopic fingerprints are obtained for bell peppers from Israel and the Netherlands. Samples from Germany, Austria, and Spain display overlapping d11B values between 0 and +12 ‰. Bell peppers from Israel show high d11B values (+28 to +35 ‰) combined with 87Sr/86Sr ratios slightly more unradiogenic than modern seawater (ca 0.7079). Bell peppers from the Netherlands, however, show low d11B values (-8 ‰) combinded with 87Sr/86Sr ratios of modern seawater (approx. 0.7085). Mainly based on diagnostic B isotopic compositions bell peppers from Israel and the Netherlands can be related to a specific geographical growing environment (Israel) or production method (Netherlands). The isotope fingerprints of bell peppers from the Netherlands are consistent with growing conditions in greenhouses typical for the Netherlands vegetable farming. Using optimized production methods crops in greenhouses were supplied with nutritients by liquid fertilizers on artificial substrates. As most fertilizers derive from non-marine salt deposits, fertilization typically imprints invariant d11B values close

  14. Boron isotopic compositions of some boron minerals

    NASA Astrophysics Data System (ADS)

    Oi, Takao; Nomura, Masao; Musashi, Masaaki; Ossaka, Tomoko; Okamoto, Makoto; Kakihana, Hidetake

    1989-12-01

    Boron minerals that have different structural formulae but are supposed to have the same geologic origin have been collected and analyzed for the 11B /10B isotopic ratio. It has been reconfirmed that minerals of marine origin have higher 11B /10B ratios than those of nonmarine origin. It has been found that the sequence of decreasing 11B /10B values among the minerals with the same geologic origin is; borax, tincal, kernite (Na borates) > ulexite ( Na/Ca borate) > colemanite, iyoite, meyerhofferite (Ca borates). This sequence is explainable on the basis of the difference in crystal structure among the minerals. That is, minerals with higher BO 3/BO 4 ratios, (the ratio of the number of the BO 3 triangle units to the number of the BO 4 tetrahedron units in the structural formula of a mineral) have higher 11B /10B ratios.

  15. Controls over the strontium isotope composition of river water

    SciTech Connect

    Palmer, M.R. ); Edmond, J.M. )

    1992-05-01

    Strontium concentrations and isotope ratios have been measured in river and ground waters from the Granges, Orinoco, and Amazon river basins. When compared with major element concentrations, the data set has allowed a detailed examination of the controls over the strontium isotope systematics of riverine input to the oceans in the following environments: (1) typical drainage basins containing limestones, evaporites, shales, and alumino-silicate metamorphic and igneous rocks; (2) shield terrains containing no chemical or biogenic sediments; and (3) the flood plains that constitute the largest areas of many large rivers. The strontium concentration and isotope compositions of river waters are largely defined by mixing of strontium derived from limestones and evaporites with strontium derived from silicate rocks. The strontium isotope composition of the limestone end member generally lies within the Phanerozoic seawater range, which buffers the [sup 87]Sr/[sup 86]Sr ratios of major rivers. A major exception is provided by the rivers draining the Himalayas, where widescale regional metamorphism appears to have led to an enrichment in limestones of radiogenic strontium derived from coexisting silicate rocks. The strontium isotope systematics of rivers draining shield areas are controlled by the intense, transport-limited, nature of the weathering reactions, and thereby limits variations in the strontium flux from these terrains. Flood plains are only a minor source of dissolved strontium to river waters, and precipitation of soil salts in some flood plains can reduce the riverine flux of dissolved strontium to the oceans.

  16. CALCIUM ISOTOPE COMPOSITION OF METEORITES, EARTH, AND MARS

    SciTech Connect

    Simon, Justin I.; DePaolo, Donald J.; Moynier, Frederic

    2009-09-01

    The relative abundances of calcium isotopes in the mass range 40-44 were measured in primitive and differentiated meteorites and igneous rocks from Earth and Mars in search of non-mass-dependent variations that could provide clues about early solar system processes. Most bulk samples of planetary materials have calcium isotopic compositions identical with Earth's within the current resolution of about 0.01% in {sup 40}Ca/{sup 44}Ca. Possible exceptions include carbonaceous chondrites, some ordinary chondrites, and two samples of calcium-aluminum-rich inclusions, which have small excesses of {sup 40}Ca. The samples with {sup 40}Ca excesses are also known to have {sup 50}Ti and {sup 135}Ba excesses and {sup 142}Nd and {sup 144}Sm deficits. Collectively these data from refractory elements suggest that the planetary embryos represented by chondrites preserve isotopic heterogeneity that reflects different nucleosynthetic sources. No late admixture from a single nucleosynthetic source can explain all observations. The results are most compatible with variable proportions of material derived from Type II supernovae. The initial calcium isotope compositions of Earth and Mars are indistinguishable and similar to the {sup 40}Ca abundance found in some chondrites and all differentiated meteorites studied. It appears that isotopic heterogeneity in calcium was still present at the completion of disk formation but was homogenized during planetary accretion.

  17. Isotope composition and volume of Earth’s early oceans

    PubMed Central

    Pope, Emily C.; Bird, Dennis K.; Rosing, Minik T.

    2012-01-01

    Oxygen and hydrogen isotope compositions of Earth’s seawater are controlled by volatile fluxes among mantle, lithospheric (oceanic and continental crust), and atmospheric reservoirs. Throughout geologic time the oxygen mass budget was likely conserved within these Earth system reservoirs, but hydrogen’s was not, as it can escape to space. Isotopic properties of serpentine from the approximately 3.8 Ga Isua Supracrustal Belt in West Greenland are used to characterize hydrogen and oxygen isotope compositions of ancient seawater. Archaean oceans were depleted in deuterium [expressed as δD relative to Vienna standard mean ocean water (VSMOW)] by at most 25 ± 5‰, but oxygen isotope ratios were comparable to modern oceans. Mass balance of the global hydrogen budget constrains the contribution of continental growth and planetary hydrogen loss to the secular evolution of hydrogen isotope ratios in Earth’s oceans. Our calculations predict that the oceans of early Earth were up to 26% more voluminous, and atmospheric CH4 and CO2 concentrations determined from limits on hydrogen escape to space are consistent with clement conditions on Archaean Earth. PMID:22392985

  18. The chromium isotopic composition of seawater and marine carbonates

    NASA Astrophysics Data System (ADS)

    Bonnand, P.; James, R. H.; Parkinson, I. J.; Connelly, D. P.; Fairchild, I. J.

    2013-11-01

    Chromium isotopes are fractionated during redox reactions and have the potential to provide a record of changes in the oxygenation levels of the oceans in the geological past. However, Cr is a trace metal in seawater and its low concentrations make isotopic measurements challenging. Here we report the first determinations of δCr53 for seawater from open ocean (Argentine Basin) and coastal (Southampton Water) settings, using a double-spike technique. The total chromium concentration in seawater from Southampton Water is 1.85 nM, whereas the Cr content of Argentine Basin samples is 5.8-6.6 nM. The δCr53 value of seawater from the Argentine Basin is 0.491-0.556‰ in intermediate and deep waters, and varies between 0.412 and 0.664‰ in surface waters (<150 m). The δCr53 value of Southampton Water seawater is 1.505‰, which may reflect in situ reduction of Cr(VI) to Cr(III). All of our seawater samples have higher δCr53 than crustal and mantle silicates, and mass balance modelling demonstrates that river water must also be enriched in heavy Cr isotopes, indicating that Cr isotopes are fractionated during weathering and/or during transport to the oceans. We also show that the Cr isotopic composition of modern non-skeletal marine carbonates (0.640- 0.745‰) encompasses the range that we measure for Argentine Basin seawater. Thus, fractionation of Cr isotopes during precipitation of these marine carbonates is likely to be small (<0.2‰), and they have the potential to provide a record of the Cr isotopic composition of ancient seawater. Phanerozoic carbonates are also characterised by heavy δCr53 and a correlation between δCr53 and Ce/Ce* suggests that the Cr and Ce cycles in the ocean are linked.

  19. Lithium concentration and Li isotopic compositions of carbonatitic complexes

    NASA Astrophysics Data System (ADS)

    Halama, R.; McDonough, W. F.; Rudnick, R. L.; Ash, R. D.; Keller, J.; Klaudius, J.; Trumbull, R.

    2005-12-01

    To evaluate the Li isotopic signatures of the mantle sources of carbonatites and the influence of magmatic differentiation and post-magmatic processes on δ7Li, we determined the Li concentrations and isotopic compositions of carbonatites and spatially associated silicate rocks, spanning a wide range in composition and age. Natrocarbonatites from Oldoinyo Lengai (1995 and 2000 eruptions) have high Li concentrations (211-292 ppm) and uniform Li isotopic signatures (δ7Li = +4.4 to +5.1 per mil). Associated silicate rocks (melilitite, nephelinite and phonolite) have lower Li concentrations (16-47 ppm) and trend towards lighter Li isotopic values (δ7Li = 0 to +3.5 per mil). Clinopyroxenes from these lavas are significantly lighter than the whole rocks by 1 to 6 per mil. Since the lavas appear to be fresh, this suggests fractionation of Li isotopes between minerals and whole rocks. In comparison to the modern natrocarbonatites, Proterozoic calciocarbonatites from Greenland (Grønnedal-Ika) and Cretaceous calciocarbonatites from Namibia (Kalkfeld) are poor in Li (< 2 ppm) and have more scattered Li isotopic compositions (δ7Li = -1 to +4 and -0.5 to +5 per mil, respectively). The lower δ7Li values may reflect contamination by crustal Li, since the low Li contents in the carbonatites make them susceptible to this. Silicate lavas from Kalkfeld have higher Li concentrations (11-12 ppm) than their associated carbonatites, but overlapping isotopic compositions (δ7Li = +4 to +6 per mil). At Grønnedal-Ika, clinopyroxene separates from nepheline syenites vary considerably in δ7Li from -6 to +5. Since Li is preferentially partitioned into fenitizing fluids [1] and an enrichment of light 6Li in fluids during degassing can be anticipated [2], the trend towards negative δ7Li can be interpreted as a result of variable interaction with metasomatizing fluids. However, fractionation of Li isotopes between minerals and melts may also have played a role. Our preliminary data

  20. The elemental and isotopic composition of galactic cosmic rays

    NASA Technical Reports Server (NTRS)

    Mewaldt, R. A.

    1982-01-01

    Galactic cosmic rays represent samples of matter from areas outside the solar system. New information regarding the elemental composition of cosmic rays has been obtained in connection with the French-Danish experiment on HEA0-3 and recent balloon experiments. The energy dependence of the source composition is considered along with a comparison of cosmic ray and solar system abundances, and the N-14 source abundance. Attention is given to cosmic ray clocks and the Mn-54 problem, advances concerning cross section measurements, and cosmic ray isotopes. The considered new observations suggest that cosmic ray elemental abundance differences from the solar system continue to be ordered by atomic parameters such as first ionization potential, at least up through Z equals 40. The isotopic composition of the cosmic ray source is found to be unlike that of the solar system.

  1. The abundance and isotopic composition of water in eucrites

    NASA Astrophysics Data System (ADS)

    Barrett, T. J.; Barnes, J. J.; TartèSe, R.; Anand, M.; Franchi, I. A.; Greenwood, R. C.; Charlier, B. L. A.; Grady, M. M.

    2016-05-01

    Volatile elements play a key role in the dynamics of planetary evolution. Extensive work has been carried out to determine the abundance, distribution, and source(s) of volatiles in planetary bodies such as the Earth, Moon, and Mars. A recent study showed that the water in apatite from eucrites has similar hydrogen isotopic compositions compared to water in terrestrial rocks and carbonaceous chondrites, suggesting that water accreted very early in the inner solar system given the ancient crystallization ages (~4.5 Ga) of eucrites. Here, the measurements of water (reported as equivalent H2O abundances) and the hydrogen isotopic composition (δD) of apatite from five basaltic eucrites and one cumulate eucrite are reported. Apatite H2O abundances range from ~30 to ~3500 ppm and are associated with a weighted average δD value of -34 ± 67‰. No systematic variations or correlations are observed in H2O abundance or δD value with eucrite geochemical trend or metamorphic grade. These results extend the range of previously published hydrogen isotope data for eucrites and confirm the striking homogeneity in the H-isotopic composition of water in eucrites, which is consistent with a common source for water in the inner solar system.

  2. The abundance and isotopic composition of water in eucrites

    NASA Astrophysics Data System (ADS)

    Barrett, T. J.; Barnes, J. J.; TartèSe, R.; Anand, M.; Franchi, I. A.; Greenwood, R. C.; Charlier, B. L. A.; Grady, M. M.

    2016-06-01

    Volatile elements play a key role in the dynamics of planetary evolution. Extensive work has been carried out to determine the abundance, distribution, and source(s) of volatiles in planetary bodies such as the Earth, Moon, and Mars. A recent study showed that the water in apatite from eucrites has similar hydrogen isotopic compositions compared to water in terrestrial rocks and carbonaceous chondrites, suggesting that water accreted very early in the inner solar system given the ancient crystallization ages (~4.5 Ga) of eucrites. Here, the measurements of water (reported as equivalent H2O abundances) and the hydrogen isotopic composition (δD) of apatite from five basaltic eucrites and one cumulate eucrite are reported. Apatite H2O abundances range from ~30 to ~3500 ppm and are associated with a weighted average δD value of -34 ± 67‰. No systematic variations or correlations are observed in H2O abundance or δD value with eucrite geochemical trend or metamorphic grade. These results extend the range of previously published hydrogen isotope data for eucrites and confirm the striking homogeneity in the H-isotopic composition of water in eucrites, which is consistent with a common source for water in the inner solar system.

  3. The Chlorine Isotopic Composition Of Lunar UrKREEP

    NASA Technical Reports Server (NTRS)

    Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

    2016-01-01

    Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. However, the current models for the Moon’s formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon. In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes, using NanoSIMS (Nanoscale Secondary Ion Mass Spectrometry) of lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

  4. Potential Skin Regeneration Activity and Chemical Composition of Absolute from Pueraria thunbergiana Flower.

    PubMed

    Kim, Do-Yoon; Won, Kyung-Jong; Hwang, Dae-Il; Yoon, Seok Won; Lee, Su Jin; Park, Joo-Hoon; Yoon, Myeong Sik; Kim, Bokyung; Lee, Hwan Myung

    2015-11-01

    The flower of Pueraria thunbergiana BENTH (PTBF) contains isoflavonoids and essential oil components. It has many biological and pharmacological activities, including anti-diabetes, anti-oxidant, and weight loss. However, its effect on skin regeneration remains unknown. In the present study, we isolated the absolute from PTBF through solvent extraction and determined the role of the absolute on skin regeneration-associated responses in human epidermal-keratinocytes (HaCats). The PTBF absolute, which contained 10 compounds, stimulated migration and proliferation and increased the phosphorylation of serine/threonine-specific protein kinase and extracellular signal-regulated kinasel/2 in HaCats. It induced type I and IV collagen synthesis in HaCats. In addition, treatment with PTBF absolute resulted in increased sprout outgrowth in HaCats. These findings suggest that PTBF absolute may participate in skin regeneration, probably through promotion of migration, proliferation, and collagen synthesis. PMID:26749850

  5. Isotopic composition of hydrogen in insoluble organic matter from cherts

    NASA Technical Reports Server (NTRS)

    Krishnamurthy, R. V.; Epstein, S.

    1991-01-01

    Robert (1989) reported the presence of unusually enriched hydrogen in the insoluble HF-HCl residue extracted from two chert samples of Eocene and Pliocene ages. Since the presence of heavy hydrogen might be due to the incorporation of extraterrestrial materials, we desired to reexamine the same samples to isolate the D-rich components. Our experiments did not reveal any D-rich components, but the hydrogen isotope composition of the insoluble residue of the two chert samples was well within the range expected for terrestrial organic matter. We also describe a protocol that needs to be followed in the hydrogen isotope analysis of any insoluble organic matter.

  6. The isotopic composition of solar flare accelerated neon

    NASA Technical Reports Server (NTRS)

    Mewaldt, R. A.; Spalding, J. D.; Stone, E. C.; Vogt, R. E.

    1979-01-01

    The individual isotopes of neon in energetic solar-flare particles have been clearly resolved with a rms mass resolution of 0.20 amu. The ratios found are Ne-20/Ne-22 = 7.6 (+2.0, -1.8) and Ne-21/Ne-22 of no more than about 0.11 in the 11-26 MeV per nucleon interval. This isotopic composition is essentially the same as that of meteoritic planetary neon-A and is significantly different from that of the solar wind.

  7. Osmium Isotope and Highly Siderophile Element Compositions of Lunar Orange and Green Glasses

    NASA Technical Reports Server (NTRS)

    Walker, R. J.; Horan, M. F.; Shearer, C. K.; Papike, J. J.

    2003-01-01

    The absolute and relative abundances of the highly siderophile elements (HSE) present in planetary mantles are primarily controlled by: 1) silicate-metal partitioning during core-mantle differentiation, 2) the subsequent addition of HSE to mantles via continued planetary accretion. Consequently, constraints on the absolute and relative abundances of the HSE in the lunar mantle will provide unique insights to the formation and late accretionary history of not only the Moon, but also Earth. Determining the HSE content of the lunar mantle, however, has proven difficult, because no bona fide mantle rocks have been collected from the moon. The only materials presently available for constraining mantle abundances are lunar volcanic rocks. Lunar basalts typically have very low concentrations of HSE and highly fractionated HSE patterns. Because of our extremely limited understanding of mantle melt partitioning of the HSE, even for terrestrial systems, extrapolations to mantle compositions from basaltic compositions are difficult, except possibly for the less compatible HSE Pt and Pd. Primitive, presumably less fractionated materials, such as picritic glasses are potentially more diagnostic of the lunar interior. Here we report Os isotopic composition data and Re, Os, Ir, Ru, Pt and Pd concentration data for green glass (15426,164) and orange glass (74001,1217). As with previous studies utilizing neutron activation analysis, we are examining different size fractions of the spherules to assess the role of surface condensation in the generation of the HSE abundances.

  8. Tracing anthropogenic thallium in soil using stable isotope compositions.

    PubMed

    Kersten, Michael; Xiao, Tangfu; Kreissig, Katharina; Brett, Alex; Coles, Barry J; Rehkämper, Mark

    2014-08-19

    Thallium stable isotope data are used in this study, for the first time, to apportion Tl contamination in soils. In the late 1970s, a cement plant near Lengerich, Germany, emitted cement kiln dust (CKD) with high Tl contents, due to cocombustion of Tl-enriched pyrite roasting waste. Locally contaminated soil profiles were obtained down to 1 m depth and the samples are in accord with a binary mixing relationship in a diagram of Tl isotope compositions (expressed as ε(205)Tl, the deviation of the (205)Tl/(203)Tl ratio of a sample from the NIST SRM 997 Tl isotope standard in parts per 10(4)) versus 1/[Tl]. The inferred mixing endmembers are the geogenic background, as defined by isotopically light soils at depth (ε(205)Tl ≈ -4), and the Tl emissions, which produce Tl-enriched topsoils with ε(205)Tl as high as ±0. The latter interpretation is supported by analyses of the CKD, which is also characterized by ε(205)Tl ≈ ± 0, and the same ε(205)Tl value was found for a pyrite from the deposit that produced the cocombusted pyrite roasting waste. Additional measurements for samples from a locality in China, with outcrops of Tl sulfide mineralization and associated high natural Tl backgrounds, reveal significant isotope fractionation between soils (ε(205)Tl ≈ +0.4) and locally grown green cabbage (ε(205)Tl between -2.5 and -5.4). This demonstrates that biological isotope fractionation cannot explain the isotopically heavy Tl in the Lengerich topsoils and the latter are therefore clearly due to anthropogenic Tl emissions from cement processing. Our results thus establish that isotopic data can reinforce receptor modeling for the toxic trace metal Tl. PMID:25055714

  9. Boron isotopic compositions of some boron minerals

    SciTech Connect

    Oi, Takao; Musashi, Masaaki; Ossaka, Tomoko; Kakihana, Hidetake ); Nomura, Masao; Okamoto, Makoto )

    1989-12-01

    Boron minerals that have different structural formulae but are supposed to have the same geologic origin have been collected and analyzed for the {sup 11}B/{sup 10}B isotopic ratio. It has been reconfirmed that minerals of marine origin have higher {sup 11}B/{sup 10}B ratios than those of nonmarine origin. It has been found that the sequence of decreasing {sup 11}B/{sup 10}B values among the minerals with the same geologic origin is; borax, tincal, kernite (Na borates) > ulexite (Na/Ca borate) > colemanite, iyoite, meyerhofferite (Ca borates). This sequence is explainable on the basis of the difference in crystal structure among the minerals. That is, minerals with high BO{sub 3}/BO{sub 4} ratios, (the ratio of the number of the BO{sub 3} triangle units to the number of the BO{sub 4} tetrahedron units in the structural formula of a mineral) have higher {sup 11}B/{sup 10}B ratios.

  10. Unnatural Isotopic Composition of Lithium Reagents

    USGS Publications Warehouse

    Qi, H.P.; Coplen, T.B.; Wang, Q. Zh; Wang, Y.-H.

    1997-01-01

    Isotopic analysis of 39 lithium reagents from several manufacturers indicates that seven were artificially depleted in 6Li significantly in excess of the variation found in terrestrial materials. The atomic weight of lithium in analyzed reagents ranged from 6.939 to 6.996, and ??7-Li, reported relative to L-SVEC lithium carbonate, ranged from -11 to +3013???. This investigation indicates that 6Li-depleted reagents are now found on chemists' shelves, and the labels of these 6Li-depleted reagents do not accurately reflect the atomic and (or) molecular weights of these reagents. In 1993, IUPAC issued the following statement: "Commercially available Li materials have atomic weights that range between 6.94 and 6.99; if a more accurate value is required, it must be determined for the specific material." This statement has been found to be incorrect In two of the 39 samples analyzed, the atomic weight of Li was in excess of 6.99.

  11. The Chlorine Isotopic Composition Of Lunar UrKREEP

    NASA Technical Reports Server (NTRS)

    Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

    2016-01-01

    Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. Numerous studies have examined the abundances and isotopic compositions of volatiles in lunar apatite, Ca5(PO4)3(F,Cl,OH). In particular, apatite has been used as a tool for assessing the sources of H2O in the lunar interior. However, current models for the Moon's formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. For ex-ample, in the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs (Rare Earth Elements), and P, collectively called KREEP, and in its primitive form - urKREEP, given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon (BSM). In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes in lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

  12. The Li isotope composition of modern biogenic carbonates

    NASA Astrophysics Data System (ADS)

    Dellinger, M.; West, A. J.; Adkins, J. F.; Paris, G.; Eagle, R.; Freitas, P. S.; Bagard, M. L.; Ries, J. B.; Corsetti, F. A.; Pogge von Strandmann, P.; Ullmann, C. V.

    2015-12-01

    The lithium stable isotope composition (δ7Li) of sedimentary carbonates has great potential to unravel weathering rates and intensity in the past, with implications for understanding the carbon cycle over geologic time. However, so far very little is known about the potential influence of fractionation of the stable Li isotope composition of biogenic carbonates. Here, we investigate the δ7Li of various organisms (particularly mollusks, echinoderms and brachiopods) abundant in the Phanerozoic record, in order to understand which geologic archives might provide the best targets for reconstructing past seawater composition. The range of measured samples includes (i) modern calcite and aragonite shells from variable natural environments, (ii) shells from organisms grown under controlled conditions (temperature, salinity, pCO2), and (iii) fossil shells from a range of species collected from Miocene deposits. When possible, both the inner and outer layers of bivalves were micro-sampled to assess the intra-shell heterogeneity. For calcitic shells, the measured δ7Li of bivalve species range from +32 to +41‰ and is systematically enriched in the heavy isotope relative to seawater (31 ‰) and to inorganic calcite, which is characterized by Δ7Licalcite-seawater = -2 to -5‰ [1]. The Li isotope composition of aragonitic bivalves, ranging from +16 to +22‰, is slightly fractionated to both high and low δ7Li relative to inorganic aragonite. The largest intra-shell Li isotope variability is observed for mixed calcite-aragonite shells (more than 20‰) whereas in single mineralogy shells, intra-shell δ7Li variability is generally less than 3‰. Overall, these results suggest a strong influence of vital effects on Li isotopes during bio-calcification of bivalve shells. On the contrary, measured brachiopods systematically exhibit fractionation that is very similar to inorganic calcite, with a mean δ7Li of 27.0±1.5‰, suggesting that brachiopods may provide good

  13. Effect of Plant Uptake on Perchlorate Isotopic Composition

    NASA Astrophysics Data System (ADS)

    Estrada, N. L.; Jackson, W. A.; Bohlke, J. K.; Sturchio, N. C.; Gu, B.; Rao, B.; Hatzinger, P. B.; Harvey, G.; Burkey, K.; McGrath, M. T.; Sevanthi, R.

    2013-12-01

    The occurrence of perchlorate (ClO4-) in the environment is attributed to both synthetic and natural sources. Unlike anthropogenic ClO4-, natural ClO4- exhibits a wide range in isotopic compositions, suggesting that natural ClO4- is formed through more than one pathway and/or undergoes post-depositional isotopic fractionation processes. One of these processes could be plant uptake and metabolism. Plants are known to reversibly accumulate ClO4-. However, there is little information available regarding the ability for plants to isotopically fractionate ClO4-. Plants could alter ClO4-isotopic composition either by mass dependent fractionation via transport carriers in the root, diffusion limitations through the root, translocation within the plant, reduction of ClO4- by plant enzymes, or non-specific exchange of oxygen in ClO4- catalyzed by plant compounds/processes. We examined the potential for plants to alter the isotopic composition of ClO4- (δ37Cl, δ18O, and Δ17O) in both hydroponic and field scale experiments. Hydroponically grown snap bean plants were exposed to variable ClO4-concentrations (2mg/L and 10mg/L) in solutions prepared from ClO4- with both normal and anomalous O isotopic abundances. At maturity, we evaluated the uptake of ClO4-relative to other anions and the isotopic compositions of ClO4- in both plants and growth solutions. Additional experiments involved field scale exposures of snap beans to irrigation water containing low levels (< 10 ug/L) of ClO4-. The majority of the initial mass of ClO4- for both the low and high exposure hydroponic treatments was recovered in the growth solutions (20-40%) or plant compartments (40-60%), while some mass was not recovered (~20%). ClO4- isotopic compositions were essentially identical between recovered ClO4- in the plant tissues and hydroponic solutions. Anion ratios indicate that ClO4-was accumulated similarly to NO3- but preferentially to Cl- (~4X). In field experiments, the isotopic composition of ClO4

  14. Do foraminifera accurately record seawater neodymium isotope composition?

    NASA Astrophysics Data System (ADS)

    Scrivner, Adam; Skinner, Luke; Vance, Derek

    2010-05-01

    Palaeoclimate studies involving the reconstruction of past Atlantic meridional overturning circulation increasingly employ isotopes of neodymium (Nd), measured on a variety of sample media (Frank, 2002). In the open ocean, Nd isotopes are a conservative tracer of water mass mixing and are unaffected by biological and low-temperature fractionation processes (Piepgras and Wasserburg, 1987; Lacan and Jeandel, 2005). For decades, benthic foraminifera have been widely utilised in stable isotope and geochemical studies, but have only recently begun to be exploited as a widely distributed, high-resolution Nd isotope archive (Klevenz et al., 2008), potentially circumventing the difficulties associated with other methods used to recover past deep-water Nd isotopes (Klevenz et al., 2008; Rutberg et al., 2000; Tachikawa et al., 2004). Thus far, a single pilot study (Klevenz et al., 2008) has indicated that core-top sedimentary benthic foraminifera record a Nd isotope composition in agreement with the nearest available bottom seawater data, and has suggested that this archive is potentially useful on both millennial and million-year timescales. Here we present seawater and proximal core-top foraminifer Nd isotope data for samples recovered during the 2008 "RETRO" cruise of the Marion Dufresne. The foraminifer samples comprise a depth-transect spanning 3000m of the water column in the Angola Basin and permit a direct comparison between high-resolution water column and core-top foraminiferal Nd isotope data. We use these data to assess the reliability of both planktonic and benthic foraminifera as recorders of water column neodymium isotope composition. Frank, M., 2002. Radiogenic isotopes: Tracers of past ocean circulation and erosional input, Rev. Geophys., 40 (1), 1001, doi:10.1029/2000RG000094. Klevenz, V., Vance, D., Schmidt, D.N., and Mezger, K., 2008. Neodymium isotopes in benthic foraminifera: Core-top systematics and a down-core record from the Neogene south Atlantic

  15. Stable isotopic composition of bottled mineral waters from Romania

    NASA Astrophysics Data System (ADS)

    Bădăluţă, Carmen; Nagavciuc, Viorica; Perșoiu, Aurel

    2015-04-01

    Romania has a high potential of mineral waters resources, featuring one of the largest mineral resources at European and global level. In the last decade, due to increased in consumption of bottled water, numerous brands have appeared on the market, with equally numerous and variable sources of provenance. In this study we have analyzed the isotopic composition of bottled mineral waters from Romania in order to determine their source and authenticity. We have analysed 32 carbonated and 24 non-carbonated mineral waters from Romania. and the results were analysed in comparison with stable isotope data from precipitation and river waters. Generally, the isotopic values of the mineral waters follow those in precipitation; however, differences occur in former volcanic regions (due to deep circulation of meteoric waters and increased exchange with host rock and volcanic CO2), as well as in mountainous regions, where high-altitude recharge occurs.

  16. The chromium isotope composition of reducing and oxic marine sediments

    NASA Astrophysics Data System (ADS)

    Gueguen, Bleuenn; Reinhard, Christopher T.; Algeo, Thomas J.; Peterson, Larry C.; Nielsen, Sune G.; Wang, Xiangli; Rowe, Harry; Planavsky, Noah J.

    2016-07-01

    The chromium (Cr) isotope composition of marine sediments has the potential to provide new insights into the evolution of Earth-surface redox conditions. There are significant but poorly constrained isotope fractionations associated with oxidative subaerial weathering and riverine transport, the major source of seawater Cr, and with partial Cr reduction during burial in marine sediments, the major sink for seawater Cr. A more comprehensive understanding of these processes is needed to establish global Cr isotope mass balance and to gauge the utility of Cr isotopes as a paleoredox proxy. For these purposes, we investigated the Cr isotope composition of reducing sediments from the upwelling zone of the Peru Margin and the deep Cariaco Basin. Chromium is present in marine sediments in both detrital and authigenic phases, and to estimate the isotopic composition of the authigenic fraction, we measured δ53Cr on a weakly acid-leached fraction in addition to the bulk sediment. In an effort to examine potential variability in the Cr isotope composition of the detrital fraction, we also measured δ53Cr on a variety of oxic marine sediments that contain minimal authigenic Cr. The average δ53Cr value of the oxic sediments examined here is -0.05 ± 0.10‰ (2σ, n = 25), which is within the range of δ53Cr values characteristic of the bulk silicate Earth. This implies that uncertainty in estimates of authigenic δ53Cr values based on bulk sediment analyses is mainly linked to estimation of the ratio of Cr in detrital versus authigenic phases, rather than to the Cr-isotopic composition of the detrital pool. Leaches of Cariaco Basin sediments have an average δ53Cr value of +0.38 ± 0.10‰ (2σ, n = 7), which shows no dependency on sample location within the basin and is close to that of Atlantic deepwater Cr (∼+0.5‰). This suggests that authigenic Cr in anoxic sediments may reliably reflect the first-order Cr isotope composition of deepwaters. For Peru Margin samples

  17. Controls over the strontium isotope composition of river water

    NASA Astrophysics Data System (ADS)

    Palmer, M. R.; Edmond, J. M.

    1992-05-01

    Strontium concentrations and isotope ratios have been measured in river and ground waters from the Ganges, Orinoco, and Amazon river basins. When compared with major element concentrations, the data set has allowed a detailed examination of the controls over the strontium isotope systematics of riverine input to the oceans in the following environments: (1) "typical" drainage basins containing limestones, evaporites, shales, and alumino-silicate metamorphic and igneous rocks; (2) shield terrains containing no chemical or biogenic sediments; and (3) the floodplains that constitute the largest areas of many large rivers. The strontium concentration and isotope composition of river waters are largely defined by mixing of strontium derived from limestones and evaporites with strontium derived from silicate rocks. The strontium isotope composition of the limestone endmember generally lies within the Phanerozoic seawater range, which buffers the 87Sr /86Sr ratios of major rivers. A major exception is provided by the rivers draining the Himalayas, where widescale regional metamorphism appears to have led to an enrichment in limestones of radiogenic strontium derived from coexisting silicate rocks. The strontium isotope systematics of rivers draining shield areas are controlled by the intense, transportlimited, nature of the weathering reactions, and thereby limits variations in the strontium flux from these terrains. Floodplains are only a minor source of dissolved strontium to river waters, and precipitation of soil salts in some floodplains can reduce the riverine flux of dissolved strontium to the oceans. The most effective mechanisms for altering the isotope ratio and flux of riverine strontium to the oceans are increased glaciation and large-scale regional metamorphism of the type produced during continental collision. Both mechanisms provide a means for increasing the 87Sr /86Sr ratio of the global riverine flux.

  18. Groundwater changes in evaporating basins using gypsum crystals' isotopic compositions

    NASA Astrophysics Data System (ADS)

    Gatti, E.; Bustos, D.; Allwood, A.; Coleman, M. L.

    2014-12-01

    While the dynamics of groundwater evaporation are well known, it is still challenging to reconstruct the water patterns in areas where water is not available anymore. We selected a specific location in White Sands National Monument (WSNM), New Mexico, to validate a method to extract information from hydrated minerals regarding past groundwater evaporation patterns in evaporitic basins. WSNM has gypsum (CaSO4.2H2O) dunes and crystals precipitated from the evaporation of an ancient lake. Our approach aims to extract the water of crystallization of gypsum and measure its oxygen and hydrogen isotopic compositions, in order to reconstruct the groundwater history of the area. The idea is that as the mother brine evaporates its isotopic composition changes continuously, recorded as water of crystallization in successive growth zones of gypsum. To check if the isotopic composition of the salt could effectively differentiate between distinctive humidity conditions, the methodology was tested first on synthetic gypsum grown under controlled humidity and temperature conditions. T and RH% were maintained constant in a glove box and precipitated gypsum was harvested every 24 hours. d2H and d18O of water of crystallization from the synthetic gypsum was extracted using a specially developed technique on a TC/EA. The brine was measured using a Gas Bench II for d18O and an H-Device for d2H on a Thermo Finnigan MAT 253 mass spectrometer. With the method tested, we measured natural gypsum. In order to identify the growth zones we mapped the surface of the crystals using an experimental space flight XRF instrument. Crystals were then sampled for isotopic analyses. Preliminary results suggest that site-specific groundwater changes can be described by the isotopic variations. We will show that the methodology is a reliable and fast method to quantify hydrological changes in a targeted environment. The study is currently ongoing but the full dataset will be presented at the conference.

  19. The Stable Isotopic Composition of Atmospheric CO2

    NASA Astrophysics Data System (ADS)

    Yakir, D.

    2003-12-01

    When a bean leaf was sealed in a closed chamber under a lamp (Rooney, 1988), in two hours the atmospheric CO2 in the microcosm reached an isotopic steady state with a 13C abundance astonishingly similar to the global mean value of atmospheric CO2 at that time (-7.5‰ in the δ13C notation introduced below). Almost concurrently, another research group sealed a suspension of asparagus cells in a different type of microcosm in which within about two hours the atmospheric O2 reached an isotopic steady state with 18O enrichment relative to water in the microcosm that was, too, remarkably similar to the global-scale offset between atmospheric O2 and mean ocean water (21‰ versus 23.5‰ in the δ18O notation introduced below; Guy et al., 1987). These classic experiments capture some of the foundations underlying the isotopic composition of atmospheric CO2 and O2. First, in both cases the biological system rapidly imposed a unique isotopic value on the microcosms' atmosphere via their massive photosynthetic and respiratory exchange of CO2 and O2. Second, in both cases the biological system acted on materials with isotopic signals previously formed by the global carbon and hydrological cycles. That is, the bean leaf introduced its previously formed organic matter (the source of the CO2 respired into microcosm's atmosphere), and the asparagus cells were introduced complete with local tap water (from which photosynthesis released molecular oxygen). Therefore, while the isotopic composition of the biological system used was slave to long-term processes, intense metabolic processes centered on few specific enzymes (Yakir, 2002) dictated the short-term atmospheric composition.In a similar vein, on geological timescales of millions of years, the atmosphere and its isotopic composition are integral parts of essentially a single dynamic ocean-atmosphere-biosphere system. This dynamic system exchanges material, such as carbon and oxygen, with the sediments and the lithosphere via

  20. The mercury isotope composition of Arctic coastal seawater

    NASA Astrophysics Data System (ADS)

    Štrok, Marko; Baya, Pascale Anabelle; Hintelmann, Holger

    2015-11-01

    For the first time, Hg isotope composition of seawater in the Canadian Arctic Archipelago is reported. Hg was pre-concentrated from large volumes of seawater sampling using anion exchange resins onboard the research vessel immediately after collection. Elution of Hg was performed in laboratory followed by isotope composition determination by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). For comparison, seawater from two stations was shipped to the laboratory and processed within it. Results showed negative mass-dependent fractionation in the range from -2.85 to -1.10‰ for δ202Hg, as well as slightly positive mass-independent fractionation of odd Hg isotopes. Positive mass-independent fractionation of 200Hg was also observed. Samples that were pre-concentrated in the laboratory showed different Hg isotope signatures and this is most probably due to the abiotic reduction of Hg in the dark by organic matter during storage and shipment after sampling. This emphasizes the need for immediate onboard pre-concentration.

  1. Isotopic composition of lithium, potassium, rubidium, and strontium in lunar surface material

    NASA Technical Reports Server (NTRS)

    Zaslavskiy, V. G.; Levskiy, L. K.; Murin, A. N.

    1974-01-01

    The isotopic composition of alkali and alkaline earth elements in the Luna 16 regolith was investigated by the method of thermionic emission, without chemical separation. The isotopic composition of the lithium in two regolith samples did not differ (within the limits 0.5 percent) from the mean of the terrestrial reference standard. At the same time, the observed difference (1 percent) in the isotopic composition of lithium between the samples requires further investigation and confirmation. The isotopic compositions of K and Rb did not differ within the limits of experimental error from the isotopic composition of the reference standard.

  2. Mass Independent Isotopic Compositions of Aerosol Sulfate and Nitrates

    NASA Astrophysics Data System (ADS)

    Thiemens, M. H.

    2001-12-01

    For nearly a half-century stable isotope ratio measurements have been utilized as a tool to understand sources, fates, and transformation mechanisms of atmospheric molecules. Carbon and oxygen (δ 13C and δ 18O) measurements of CO2 have been instrumental in providing specific details of the carbon cycle. Without these measurements, understanding of the carbon cycle and transfer rates between reservoirs would be considerably diminished. Deuterium and oxygen isotopic measurements of atmospheric water has similarly enhanced the ability to model the atmospheric and geochemical recycling of the hydrologic cycle. Other molecules investigated include, for example, CO, CH4, N2O, SO4, NH, and Cl. The ability to interpret these high precision isotope ratio measurements relies upon a fundamental understanding of the basic physical-chemical processes which produce the alteration of the stable isotope ratio. Such processes typically include thermodynamics (viz a viz isotope exchange), kinetics, and evaporation-condensation. Though the mechanism by which these alterations occur, they all depend in some fashion upon mass differences in the isotopically substituted atoms. In 1983, Thiemens and Heidenreich (1) demonstrated that a chemical process is capable of producing an alteration of stable isotopes which was independent of mass. Subsequent to that time, it has been shown that measurements of mass independent isotopic compositions provide a new view of atmospheric process which may not be derived from single isotope ratio measurements (reviews by (2), (3)). In the past few years, mass independent isotopic compositions have been utilized to understand ancient atmospheres on both Earth and Mars (review by (4)). It has been known for decades that atmospheric sulfate is an extraordinary species. It participates in climate change in its capacity as a cloud condensation nuclei and it is a human and environmental health hazard. By the same token, aerosol nitrate is an environmental

  3. Oxygen isotopic composition of opaline phytoliths: Potential for terrestrial climatic reconstruction

    SciTech Connect

    Shahack-Gross, R.; Weiner, S.; Shemesh, A.; Yakir, D.

    1996-10-01

    Opaline mineralized bodies are produced by many terrestrial plants and accumulate in certain soils and archaeological sites. Analyses of the oxygen isotopic compositions of these so-called phytoliths from stems and leaves of wheat plants grown in a greenhouse showed a linear relationship with stem and leaf water isotopic compositions and hence, indirectly, rain water isotopic composition. Analyses of wheat plants grown in fields showed that stem phytoliths isotopic composition directly reflects the seasonal air temperature change, whereas leaf phytoliths isotopic composition reflects both temperature and relative humidity. Temperature and the oxygen isotopic composition of stem phytoliths were related by an equation similar to that proposed for marine opal. Oxygen isotopic compositions of fossil phytoliths, and in particular those from stems, could be valuable for reconstructing past terrestrial climate change.

  4. The Abundance and Isotopic Composition of Hg in Extraterrestrial Materials

    NASA Technical Reports Server (NTRS)

    Lauretta, D. S.

    2004-01-01

    During the past three year grant period we made excellent progress in our study of the abundances and isotopic compositions of Hg and other volatile trace elements in extraterrestrial materials. As part of my startup package I received funds to construct a state-of-the-art experimental facility to study gas-solid reaction kinetics. Much of our effort was spent developing the methodology to measure the abundance and isotopic composition of Hg at ultratrace levels in solid materials. In our first study, the abundance and isotopic composition of Hg was determined in bulk samples of the Murchison (CM) and Allende (CV) carbonaceous chondrites. We have continued our study of mercury in primitive meteorites and expanded the suite of meteorites to include other members of the CM and CV chondrite group as well as CI and CO chondrites. Samples of the CI chondrite Orgueil, the CM chondrites Murray, Nogoya, and Cold Bokkeveld, the CO chondrites Kainsaz, Omans, and Isna, and the CV chondrites Vigarano, Mokoia, and Grosnaja were tested. We have developed a thermal analysis ICP-MS technique and applied it to the study of a suite of thermally labile elements (Zn, As, Se, Cd, In, Sn, Sb, Te, Hg, Au, Tl, Pb, and Bi) in geologic materials as well.

  5. Alkali elemental and potassium isotopic compositions of Semarkona chondrules

    USGS Publications Warehouse

    Alexander, C.M. O'D.; Grossman, J.N.

    2005-01-01

    We report measurements of K isotope ratios in 28 Semarkona chondrules with a wide range of petrologic types and bulk compositions as well as the compositions of CPX-mesostasis pairs in 17 type I Semarkona chondrules, including two chondrules with radial alkali zonation and 19 type II chondrules. Despite the wide range in K/Al ratios, no systematic variations in K isotopic compositions were found. Semarkona chondrules do not record a simple history of Rayleigh-type loss of K. Experimentally determined evaporation rates suggest that considerable alkali evaporation would have occurred during chondrule formation. Nevertheless, based on Na CPX-mesostasis distribution coefficients, the alkali contents of the cores of most chondrules in Semarkona were probably established at the time of final crystallization. However, Na CPX-mesostasis distribution coefficients also show that alkali zonation in type I Semarkona chondrules was produced by entry of alkalis after solidification, probably during parent body alteration. This alkali metasomatism may have gone to completion in some chondrules. Our preferred explanation for the lack of systematic isotopic enrichments, even in alkali depleted type I chondrule cores, is that they exchanged with the ambient gas as they cooled. ?? The Meteoritical Society, 2005.

  6. Isotopic composition of precipitation during different atmospheric circulation patterns

    NASA Astrophysics Data System (ADS)

    Brenčič, Mihael; Kononova, Nina; Vreča, Polona

    2016-04-01

    Precipitation generating processes depend on atmospheric circulation patterns and consequently it is expected that its water stable isotopic composition of hydrogen and oxygen is related to them. Precipitation generated at similar atmospheric circulation patterns should have similar empirical distribution of δ2H and δ18O values. There are several approaches in which atmospheric circulation patterns are classified as elementary air circulation mechanisms - ECM; in our approach we have applied Dzerdzeevskii classification. Two types of models of relation between ECM and isotopic composition of precipitation are proposed; first is based on the linear combination of δ2H and δ18O values with precipitation amount weighted average (Brenčič et al., 2015) and the second new one is based on the multiple regression approach. Both approaches make possible also to estimate empirical distributions' dispersion parameters. Application of the models is illustrated on the precipitation records from Ljubljana and Portorož GNIP stations, Slovenia. Estimated values of the parameters for empirical distributions of δ2H and δ18O of each ECM subtype have shown that calculated estimates are reasonable. Brenčič, M., Kononova, N.K., Vreča, P., 2015: Relation between isotopic composition of precipitation and atmospheric circulation patterns. Journal of Hydrology 529, 1422-1432: doi: 10.1016/j.jhydrol.2015.08.040

  7. NBL CRM 112-A: A new certified isotopic composition

    NASA Astrophysics Data System (ADS)

    Thomas, R. B.; Essex, R. M.; Mason, P.

    2007-12-01

    NBL CRM 112-A Uranium Metal Assay Standard is commonly used as a natural uranium isotopic reference material within the earth science mass spectrometry community. The metal is from the same parent material as NBS SRM 960, the uranyl nitrate solution, CRM 145, and the high-purity uranyl nitrate solution CRM 145-B. Because CRM 112-A has not yet been certified for isotopic composition, it has been assumed that this material has a natural 235U/238U (0.0072527), and the δ234U has been determined by measurement (e.g. -37.1‰; Cheng et al., 2000). These values have been widely used to calibrate the concentration of spikes and standards, and to correct measurements for instrument or mass bias. New, preliminary, isotopic measurements on CRM 145 and CRM 112-A performed at New Brunswick Laboratory suggest that these reference materials have a slightly lower 235U/238U and δ234U than have been commonly used. If this is the case, then data using the accepted values may be slightly biased. The significance of this bias will depend on the uncertainty of the measurement, how the CRM 112-A data is used to correct measurement data, the cited values that were used to correct the data, and the final certified values of the CRM. This fall, New Brunswick Laboratory is certifying the isotopic composition of the CRM 112-A metal using high precision thermal ionization mass spectrometry techniques. Upon completion of certification, the new CRM 112- A standard with certified isotopic ratios will provide the earth science community with a well characterized and traceable reference for calibrating and correcting their mass spectrometry measurement systems.

  8. Stable isotope composition of the meteoric precipitation in Croatia.

    PubMed

    Hunjak, Tamara; Lutz, Hans O; Roller-Lutz, Zvjezdana

    2013-01-01

    The precipitation is the input into the water system. Its stable isotope composition has to be known for the proper use and management of water resources. Croatia is not well represented in the Global Network of Isotopes in Precipitation (GNIP) database, and the geomorphology of the country causes specific local conditions. Therefore, at the Stable Isotope Laboratory (SILab), Rijeka, we monitor the stable isotope composition (δ(18)O, δ(2)H) of precipitation. Since δ(18)O and δ(2)H are well correlated, we concentrate the discussion on the δ(18)O distribution. Together with GNIP, our database contains 40 stations in Croatia and in the neighbouring countries. Their different latitudes, longitudes and altitudes give information of great detail, including the influence of the topographic structure on the precipitation in the south-eastern part of Europe, as well as the complex interplay of the different climate conditions in the area. Within a few hundred kilometres, the stable isotope values display a significant change from the maritime character in the south (mean δ(18)O around-6 to-8‰) to the continental behaviour in the north (mean δ(18)O around-8 to-11‰). Depending on the location, the mean δ(18)O values vary with altitude at a rate of approximately-0.2‰/100 m and-0.4‰/100 m, respectively. Also the deuterium excess has been found to depend on location and altitude. The data are being used to construct a δ(18)O map for the entire area. PMID:23937110

  9. Magnesium stable isotope composition of Earth's upper mantle

    NASA Astrophysics Data System (ADS)

    Handler, Monica R.; Baker, Joel A.; Schiller, Martin; Bennett, Vickie C.; Yaxley, Gregory M.

    2009-05-01

    The mantle is Earth's largest reservoir of Mg containing > 99% of Earth's Mg inventory. However, no consensus exists on the stable Mg isotope composition of the Earth's mantle or how variable it is and, in particular, whether the mantle has the same stable Mg isotope composition as chondrite meteorites. We have determined the Mg isotope composition of olivine from 22 mantle peridotites from eastern Australia, west Antarctica, Jordan, Yemen and southwest Greenland by pseudo-high-resolution MC-ICP-MS on Mg purified to > 99%. The samples include fertile lherzolites, depleted harzburgites and dunites, cryptically metasomatised ('dry') peridotites and modally metasomatised apatite ± amphibole-bearing harzburgites and wehrlites. Olivine from these samples of early Archaean through to Permian lithospheric mantle have δ25Mg DSM-3 = - 0.22 to - 0.08‰. These data indicate the bulk upper mantle as represented by peridotite olivine is homogeneous within current analytical uncertainties (external reproducibility ≤ ± 0.07‰ [2 sd]). We find no systematic δ25Mg variations with location, lithospheric age, peridotite fertility, or degree or nature of mantle metasomatism. Although pyroxene may have slightly heavier δ25Mg than coexisting olivine, any fractionation between mantle pyroxene and olivine is also within current analytical uncertainties with a mean Δ25Mg pyr-ol = +0.06 ± 0.10‰ (2 sd; n = 5). Our average mantle olivine δ25Mg DSM-3 = - 0.14 ± 0.07‰ and δ26Mg DSM-3 = - 0.27 ± 0.14‰ (2 sd) are indistinguishable from the average of data previously reported for terrestrial basalts, confirming that basalts have stable Mg isotope compositions representative of the mantle. Olivine from five pallasite meteorites have δ25Mg DSM-3 = - 0.16 to - 0.11‰ that are identical to terrestrial olivine and indistinguishable from the average δ25Mg previously reported for chondrites. These data provide no evidence for measurable heterogeneity in the stable Mg isotope

  10. Probing the Isotopic Composition of Surface Waters Across Isotopic Extremes of Cryogenian Carbonates

    NASA Astrophysics Data System (ADS)

    Bosak, T.; Matys, E. D.; Bird, L. R.; Macdonald, F. A.; Freeman, K. H.

    2012-12-01

    Neoproterozoic carbonate strata record unusually large and positive carbon isotope values (δ13Ccarb from 4 to 10 per mil), and stratigraphically extensive large negative carbon isotope excursions (δ13Ccarb < -5 per mil). Mechanisms that account for the magnitude, the facies distribution and the global abundance of these isotopically extreme carbonates in Neoproterozoic successions remain poorly understood. Little is also known about organisms and metabolisms that cycled carbon in these carbonate strata, because they rarely contain well-preserved organic-rich fossils. To better understand the cycling of carbon during the deposition of the 715-635 Ma Tayshir member of the Tsagaan Oloom Formation, Mongolia, we analyzed δ13Cfossil of two types of organic fossils that occur in 13C- enriched carbonates (+ 5 to 9.9 per mil) and within 13C-depleted carbonates of the Tayshir anomaly (-3 to -6 per mil). Because these organic microfossils are remarkably similar to the tests of modern planktonic, herbivorous tintinnid ciliates and benthic macroscopic red algae, respectively, they can be used as tracers of organic matter production in surface waters. Fossil tests were extracted by acid maceration, cleaned and analyzed morphologically and microscopically. Their carbon isotopic composition was measured using a nano-scaled elemental analyzer inlet (nano-EA-IRMS), with ±1 per mil analytical precision. To date, we analyzed 12 samples of 100-150 organic tests, representing 3 different fossiliferous parts of the Tayshir anomaly (δ13Ccarb < -3 per mil) and 3 different strata predating the Tayshir anomaly (δ13Ccarb > +5 per mil), respectively. More samples, including those of fossil algae and tests from the carbonate strata overlying the Tayshir anomaly, are currently being analyzed. Initial data reveal a rather constant isotopic composition of organic carbon in fossil tests (δ13Cfossil), with values of -23 ±1 per mil both within 13C-enriched and 13C-depleted carbonates. The

  11. The triple isotopic composition of oxygen in leaf water

    NASA Astrophysics Data System (ADS)

    Landais, A.; Barkan, E.; Yakir, D.; Luz, B.

    2006-08-01

    The isotopic composition of atmospheric O 2 depends on the rates of oxygen cycling in photosynthesis, respiration, photochemical reactions in the stratosphere and on δ17O and δ18O of ocean and leaf water. While most of the factors affecting δ17O and δ18O of air O 2 have been studied extensively in recent years, δ17O of leaf water—the substrate for all terrestrial photosynthesis—remained unknown. In order to understand the isotopic composition of atmospheric O 2 at present and in fossil air in ice cores, we studied leaf water in field experiments in Israel and in a European survey. We measured the difference in δ17O and δ18O between stem and leaf water, which is the result of isotope enrichment during transpiration. We calculated the slopes of the lines linking the isotopic compositions of stem and leaf water. The obtained slopes in ln( δ17O + 1) vs. ln( δ18O + 1) plots are characterized by very high precision (˜0.001) despite of relatively large differences between duplicates in both δ17O and δ18O (0.02-0.05‰). This is so because the errors in δ18O and δ17O are mass-dependent. The slope of the leaf transpiration process varied between 0.5111 ± 0.0013 and 0.5204 ± 0.0005, which is considerably smaller than the slope linking liquid water and vapor at equilibrium (0.529). We further found that the slope of the transpiration process decreases with atmospheric relative humidity ( h) as 0.522-0.008 × h, for h in the range 0.3-1. This slope is neither influenced by the plant species, nor by the environmental conditions where plants grow nor does it show strong variations along long leaves.

  12. Light and heavy element isotopic compositions of mainstream SiC grains.

    SciTech Connect

    Amari, S.; Clayton, R. N.; Davis, A. M.; Lewis, R. S.; Pellin, M. J.

    1999-02-03

    Although a variety of types of pre-solar SiC grains have been classified by their C, N, and Si isotopic composition, the majority of such grains are so-called mainstream grains and are believed to have come from asymptotic giant branch stars [1]. We have previously reported the Mo isotopic compositions of presolar SiC grains whose C, N, and Si isotopic compositions were not known [2]. Since most presolar SiC grains fall in the mainstream group, we assumed that these grains were mainstream. The excellent match of the Mo isotopic data with expectations for nucleosynthesis in AGB stars was consistent with this identification. In order to better understand the distribution of isotopic compositions in presolar grains, we have begun to measure heavy element isotopic compositions of presolar SiC grains of known C, N and Si isotopic composition.

  13. Silicon isotopes in granulite xenoliths: Insights into isotopic fractionation during igneous processes and the composition of the deep continental crust

    NASA Astrophysics Data System (ADS)

    Savage, Paul S.; Georg, R. Bastian; Williams, Helen M.; Halliday, Alex N.

    2013-03-01

    The silicon (Si) cycle is of great current interest but the isotopic composition of the continental crust has not been determined. Magmatic differentiation generates liquids with heavier Si and the lower crust, thought to be dominated by cumulates and restites, is predicted to have a light isotopic composition. This is borne out by the composition of many types of granite, which appear to have relative light Si for their silica content. Here we report the Si isotopic compositions of two granulite facies xenolith suites, from the Chudleigh and McBride volcanic provinces, Australia, providing new constraints on deep crustal processes and the average composition of the deep continental crust. The xenoliths display a range of isotopic compositions (δ30Si=-0.43‰ to -0.15‰) comparable to that measured previously for igneous rocks. The isotopic compositions of the McBride xenoliths reflect assimilation and fractional crystallisation (AFC) and/or partial melting processes. Silicon and O isotopes are correlated in the McBride suite and can be explained by AFC of various evolved parent melts. In contrast, the Chudleigh xenoliths have Si isotope compositions predominantly controlled by the specific mineralogy of individual cumulates. Using the xenolith data and a number of weighting methods, the Si isotope compositions of the lower and middle crust are calculated to be δ30Si=-0.29±0.04‰ (95% s.e.) and -0.23±0.04‰ (95% s.e.) respectively. These values are almost identical to the composition of the Bulk Silicate Earth, implying minimal isotope fractionation associated with continent formation and no light lower crustal reservoir.

  14. Determination of the combined isotopic composition of atmospheric methane

    NASA Astrophysics Data System (ADS)

    Butterworth, Anna Lucy

    Methane is an important global warming gas, present in the atmosphere at a concentration of 1.714 ppmv. Its concentration has more than doubled since the start of the industrial revolution and the increase is generally acknowledged to be due to human activities. The continued rise in concentration of methane is believed to be contributing to an increase in mean global temperature. Recently, the global budget of methane has been constrained by balancing the magnitude and isotopic signature of the sources and sinks with the measured tropospheric abundance and isotopic composition. The dual element stable isotopic composition (δ13C and /delta D) of methane may be used to characterise different sources of methane. Traditional methods of determining the δ13C value and the /delta D value of methane require large sample sizes. An alternative approach to investigating the stable isotopic composition of methane was to determine the combined ratio of 13CH4 and 12CH3D (mass 17) relative to 12CH4 (mass 16) and quote the results on a δ17M scale. A static-vacuum mass spectrometer has been developed specifically for the determination of the 17M/16M ratio of sub- nanomole quantities of methane with a δ17M precision of [/pm]0.2/ /perthous. An on-line sample preparation technique has also been developed to separate the methane from 10 ml of air and provide a pure, dry, ~300 picomole methane sample for isotope ratio determination. The overall δ17M precision of the analysis of the methane in air samples was [<][/pm]0.5/ /perthous. A number of sources of atmospheric methane have been investigated, demonstrating that sources may be distinguished from each other on the δ17M scale. The very small sample requirements for the instrument permitted a simple air sampling procedure to be employed, which was particularly useful for collecting air samples in remote locations. Air samples, containing methane emitted by termites, were collected from a tropical rainforest. The methane produced

  15. BOREAS TE-5 CO2 Concentration and Stable Isotope Composition

    NASA Technical Reports Server (NTRS)

    Hall, Forrest G. (Editor); Curd, Shelaine (Editor); Ehleriinger, Jim; Brooks, J. Renee; Flanagan, Larry

    2000-01-01

    The BOREAS TE-5 team collected measurements in the NSA and SSA on gas exchange, gas composition, and tree growth. This data set contains measurements of the concentration and stable carbon (C-13/C-12 and oxygen (O-18/O-16) isotope ratios of atmospheric CO2 in air samples collected at different heights within forest canopies. The data were collected to determine the influence of photosynthesis and respiration by the forest ecosystems on the concentration and stable isotope ratio of atmospheric CO2 These measurements were collected at the SSA during each 1994 IFC at OJP, OBS, and OA sites. Measurements were also collected at the NSA during each 1994 IFC at the OJP, T6R5S TE UBS, and T2Q6A TE OA sites. The stable isotope ratios are expressed using standard delta notation and in units of per mil. The isotope ratios are expressed relative to the international standard, PDB, for both carbon and oxygen samples. The data are stored in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Activity Archive Center (DAAC).

  16. Assessing the ability of isotope-enabled General Circulation Models to simulate the variability of Iceland water vapor isotopic composition

    NASA Astrophysics Data System (ADS)

    Erla Sveinbjornsdottir, Arny; Steen-Larsen, Hans Christian; Jonsson, Thorsteinn; Ritter, Francois; Riser, Camilla; Messon-Delmotte, Valerie; Bonne, Jean Louis; Dahl-Jensen, Dorthe

    2014-05-01

    During the fall of 2010 we installed an autonomous water vapor spectroscopy laser (Los Gatos Research analyzer) in a lighthouse on the Southwest coast of Iceland (63.83°N, 21.47°W). Despite initial significant problems with volcanic ash, high wind, and attack of sea gulls, the system has been continuously operational since the end of 2011 with limited down time. The system automatically performs calibration every 2 hours, which results in high accuracy and precision allowing for analysis of the second order parameter, d-excess, in the water vapor. We find a strong linear relationship between d-excess and local relative humidity (RH) when normalized to SST. The observed slope of approximately -45 o/oo/% is similar to theoretical predictions by Merlivat and Jouzel [1979] for smooth surface, but the calculated intercept is significant lower than predicted. Despite this good linear agreement with theoretical calculations, mismatches arise between the simulated seasonal cycle of water vapour isotopic composition using LMDZiso GCM nudged to large-scale winds from atmospheric analyses, and our data. The GCM is not able to capture seasonal variations in local RH, nor seasonal variations in d-excess. Based on daily data, the performance of LMDZiso to resolve day-to-day variability is measured based on the strength of the correlation coefficient between observations and model outputs. This correlation coefficient reaches ~0.8 for surface absolute humidity, but decreases to ~0.6 for δD and ~0.45 d-excess. Moreover, the magnitude of day-to-day humidity variations is also underestimated by LMDZiso, which can explain the underestimated magnitude of isotopic depletion. Finally, the simulated and observed d-excess vs. RH has similar slopes. We conclude that the under-estimation of d-excess variability may partly arise from the poor performance of the humidity simulations.

  17. Chromium isotopic composition of the implanted solar wind-bearing component in Apollo 16 lunar soils

    NASA Astrophysics Data System (ADS)

    Kitts, Bunnie Kathleen

    2002-09-01

    Chromium isotopes are scientifically interesting for many reasons. For example, 53Mn decays to 53Cr which has allowed for the development of a fine-scale chronometer, 54Cr is a neutron-rich isotope believed to be generated in Type Ia supernovae which sheds light on local nucleosynthetic processes, and variations in 53Cr may be due to incorporation of differing amounts of live 53Mn. This 53Mn may be linearly, radially heterogeneous (Lugmair and Shukolyukov, 1998). Therefore, to investigate these issues, the isotopic composition of the implanted solar wind-bearing component was measured by thermal ionization mass spectrometry of acid etches of plagioclase grains from two Apollo 16 lunar soils. Small aliquots of the etches were spiked with Cr and Ca for isotope dilution. Spiking for Ca allows for the determination of etch depth and the Cr/Ca ratio which acts as a proxy for solar wind content. From these isotope dilution data, three important observations were made. First, the etch depth is in line with the solar wind implantation depths of noble gases (e.g. Eberhardt et al., 1970). Second, the Cr/Ca ratio falls off quickly with depth, peaks in the Etch 1 fraction of 62281 at 0.0006 and 0.0009 for 60601 and returns to the lunar Cr/Ca ratio of 0.00007 by weight by Etch 5. The coronal ratio is 0.224 (Anders and Grevesse, 1989). Third, the absolute abundance of Cr peaks in Etch 1 and falls off with progressive etches. Therefore, it is inferred that the solar wind-bearing component has been successfully isolated from the background lunar signature. The isotopic composition of this component is 3.9 ± 0.4 ɛ53Cr and 8.5 ± 0.6 ɛ54Cr for 62281 and 4.5 ± 0.1 and 15.0 ± 0.3, respectively, for 60601. These data are surprising. It will be shown that contributions from contamination, spallation and isobaric interferences are unlikely to be significant. The Cr data presented here are not linearly mass-dependent. Therefore, the linear, mass-dependent processes of volatilization

  18. Isotopic composition of strontium in sea water throughout Phanerozoic time

    USGS Publications Warehouse

    Peterman, Z.E.; Hedge, C.E.; Tourtelot, H.A.

    1970-01-01

    Isotopic analyses of strontium in primary fossil carbonate reveal significant variations in Sr87 Sr86 of sea water during the Phanerozoic. The strontium isotopic composition may have been uniform from the Ordovician through the Mississippian, with an average Sr87 Sr86 of 0.7078. A subsequent decrease in this value into the Mesozoic is interrupted by two provisionally documented positive pulses in Sr87 Sr86-one in the Early Pennsylvanian and one in the Early Triassic. The lowest observed value (0.7068) occurred in Late Jurassic time, and this was followed by a gradual increase to 0.7075 in the Late Cretaceous and a more rapid increase through the Tertiary to 0.7090 for modern sea water. These variations are thought to be the result of a complex interplay of periods of intense volcanism and epeirogenic movements of the continents on a worldwide scale. ?? 1970.

  19. On the mean oxygen isotope composition of the Solar System

    NASA Astrophysics Data System (ADS)

    Ozima, M.; Podosek, F. A.; Higuchi, T.; Yin, Q.-Z.; Yamada, A.

    2007-02-01

    Since the first discovery of extraordinary oxygen isotope compositions in carbonaceous meteorites by Clayton et al. [Clayton, R.N., Grossman, L., Mayeda, T.K., 1973. Science 182, 485-488], numerous studies have been done to explain the unusual mass-independent isotope fractionation, but the problem is still unresolved to this day. Clayton's latest interpretation [Clayton, R.N., 2002. Nature 415, 860-861] sheds new light on the problem, and possible hypotheses now seem to be fairly well defined. A key issue is to resolve whether the oxygen isotopes in the Solar System represented by the Sun (solar oxygen) are the same as oxygen isotopes in planetary objects such as bulk meteorites, Mars, Earth, and Moon, or whether the solar oxygen is more similar to the lightest oxygen isotopes observed in CAIs (Calcium Aluminum-rich Inclusions) in primitive meteorites. Here, we examined the problem using oxygen isotope analytical data of about 400 bulk meteorite samples of various classes or types (data compiled by K. Lodders). We used in our discussion exclusively the parameter Δ 17O, a direct measure of the degree of mass-independent isotope fractionation of oxygen isotopes. When Δ 17O is arranged according to a characteristic size of their host planetary object, it shows a systematic trend: (1) Δ 17O values scatter around zero; (2) the scatter from the mean (Δ 17O=0) decreases with increasing representative size of the respective host planetary object. This systematic trend is easily understood on the basis of a hierarchical scenario of planetary formation, that is, larger planetary objects have formed by progressive accretion of planetesimals by random sampling over a wide spectrum of proto-solar materials. If this progressive random sampling of planetesimals were the essential process of planetary formation, the isotopic composition of planetary oxygen should approach that of the solar oxygen. To test this random sampling hypothesis, we applied a multiscale, multistep

  20. Perchlorate in the Great Lakes: isotopic composition and origin.

    PubMed

    Poghosyan, Armen; Sturchio, Neil C; Morrison, Candice G; Beloso, Abelardo D; Guan, Yunbin; Eiler, John M; Jackson, W Andrew; Hatzinger, Paul B

    2014-10-01

    Perchlorate is a persistent and mobile contaminant in the environment with both natural and anthropogenic sources. Stable isotope ratios of oxygen (δ(18)O, Δ(17)O) and chlorine (δ(37)Cl) along with the abundance of the radioactive isotope (36)Cl were used to trace perchlorate sources and behavior in the Laurentian Great Lakes. These lakes were selected for study as a likely repository of recent atmospheric perchlorate deposition. Perchlorate concentrations in the Great Lakes range from 0.05 to 0.13 μg per liter. δ(37)Cl values of perchlorate from the Great Lakes range from +3.0‰ (Lake Ontario) to +4.0‰ (Lake Superior), whereas δ(18)O values range from -4.1‰ (Lake Superior) to +4.0‰ (Lake Erie). Great Lakes perchlorate has mass-independent oxygen isotopic variations with positive Δ(17)O values (+1.6‰ to +2.7‰) divided into two distinct groups: Lake Superior (+2.7‰) and the other four lakes (∼+1.7‰). The stable isotopic results indicate that perchlorate in the Great Lakes is dominantly of natural origin, having isotopic composition resembling that measured for indigenous perchlorate from preindustrial groundwaters of the western USA. The (36)Cl/Cl ratio of perchlorate varies widely from 7.4 × 10(-12) (Lake Ontario) to 6.7 × 10(-11) (Lake Superior). These (36)ClO4(-) abundances are consistent with an atmospheric origin of perchlorate in the Great Lakes. The relatively high (36)ClO4(-) abundances in the larger lakes (Lakes Superior and Michigan) could be explained by the presence of (36)Cl-enriched perchlorate deposited during the period of elevated atmospheric (36)Cl activity following thermonuclear bomb tests in the Pacific Ocean. PMID:25171443

  1. Stable isotope composition of precipitation over southeast Asia

    NASA Astrophysics Data System (ADS)

    AraguáS-AraguáS, Luis; Froehlich, Klaus; Rozanski, Kazimierz

    1998-11-01

    Spatial and temporal variability of the stable isotope composition of precipitation in the southeast Asia and western Pacific region is discussed, with emphasis on the China territory, based on the database of the International Atomic Energy Agency/World Meteorological Organization Global Network "Isotopes in Precipitation" and the available information on the regional climatology and atmospheric circulation patterns. The meteorological and pluviometric regime of southeast Asia is controlled by five different air masses: (1) polar air mass originating in the Arctic, (2) continental air mass originating over central Asia, (3) tropical-maritime air mass originating in the northern Pacific, (4) equatorial-maritime air mass originating in the western equatorial Pacific, and (5) equatorial-maritime air mass originating in the Indian Ocean. The relative importance of different air masses in the course of a given year is modulated by the monsoon activity and the seasonal displacement of the Intertropical Convergence Zone (ITCZ). Gradual rain-out of moist, oceanic air masses moving inland, associated with monsoon circulation, constitutes a powerful mechanism capable of producing large isotopic depletions in rainfall, often completely overshadowing the dependence of δ18O and δ2H on temperature. For instance, precipitation at Lhasa station (Tibetan Plateau) during rainy period (June-September) is depleted in 18O by more than 6‰ with respect to winter rainfall, despite of 10°C higher surface air temperature in summer. This characteristic isotopic imprint of monsoon activity is seen over large areas of the region. The oceanic air masses forming the two monsoon systems, Pacific and Indian monsoon, differ in their isotope signatures, as demonstrated by the average δ18O of rainfall, which in the south of China (Haikou. Hong Kong) is about 2.5‰ more negative than in the Bay of Bengal (Yangoon). Strong seasonal variations of the deuterium excess values in precipitation

  2. Isotope Fractionation During N Mineralization and the N Isotope Composition of Terrestrial Ecosystem N Pools

    NASA Astrophysics Data System (ADS)

    Dijkstra, P.; Schwartz, E.; Hungate, B. A.; Hart, S. C.

    2008-12-01

    It has been an open question for several decades whether N mineralization is a fractionating process. This question is important for N cycling in terrestrial ecosystems because even a small fractionation during N mineralization could potentially have a large influence on the N isotope composition of other ecosystem N pools. Fractionation during N mineralization should result in a difference between the N isotope composition of the soil microorganisms, that of its substrates, and products. We analyzed the N isotope composition of the soil microbial biomass in a variety of ecosystems, and found that it was 15N enriched compared to that of other soil N pools, such as soil soluble, organic and inorganic N (Dijkstra et al. 2006a,b). We observed a negative correlation between the 15N enrichment of the microorganisms and the relative C and N availability for soil from ecosystems in Hawaii and Arizona, across a broad range of climates, grasslands and forests, and more than four million years of ecosystem development. This suggests that during N dissimilation (and associated transaminations) and N export, the lighter 14N N isotope is preferentially removed in a manner similar to that proposed for animals and ectomycorrhizae. This was further confirmed by the positive correlation between microbial 15N enrichment and net N mineralization rate (Dijkstra et al. 2008, Ecology Letters 11: 389-397) and by culture experiments with Escherichia coli (Collins et al. 2008). Since mineralization is the largest flux of N in ecosystems, fractionation during N mineralization has the potential to influence the N isotope composition of other N pools, such as inorganic N, plant N and soil organic matter N. We demonstrate that the N isotope compositions of these ecosystem N pools exhibit differences that are consistent with fractionation during N mineralization. Our results show that the N isotope composition can be used as a measure to trace N mineralization and decomposition in ecosystems

  3. Novel isotopic N, N-dimethyl leucine (iDiLeu) reagents enable absolute quantification of peptides and proteins using a standard curve approach

    PubMed Central

    Greer, Tyler; Lietz, Christopher B.; Xiang, Feng; Li, Lingjun

    2014-01-01

    Absolute quantification of protein targets using liquid chromatography-mass spectrometry (LC-MS) is a key component of candidate biomarker validation. One popular method combines multiple reaction monitoring (MRM) using a triple quadrupole instrument with stable isotope-labeled standards (SIS) for absolute quantification (AQUA). LC-MRM AQUA assays are sensitive and specific, but they are also expensive due to the cost of synthesizing stable isotope peptide standards. While the chemical modification approach using Mass Differential Tags for Relative and Absolute Quantification (mTRAQ) represents a more economical approach when quantifying large numbers of peptides, these reagents are costly and still suffer from lower throughput because only two concentration values per peptide can be obtained in a single LC-MS run. Here, we have developed and applied a set of five novel mass difference reagents, isotopic N,N-dimethyl leucine (iDiLeu). These labels contain an amine reactive group, triazine ester, are cost effective due to their synthetic simplicity, and have increased throughput compared to previous LC-MS quantification methods by allowing construction of a four-point standard curve in one run. iDiLeu-labeled peptides show remarkably similar retention time shifts, slightly lower energy thresholds for higher-energy collisional dissociation (HCD) fragmentation, and high quantification accuracy for trypsin-digested protein samples (median errors <15%). By spiking in an iDiLeu-labeled neuropeptide, allatostatin, into mouse urine matrix, two quantification methods are validated. The first uses one labeled peptide as an internal standard to normalize labeled peptide peak areas across runs (<19% error) while the second enables standard curve creation and analyte quantification in one run (<8% error). PMID:25377360

  4. Novel isotopic N, N-Dimethyl Leucine (iDiLeu) Reagents Enable Absolute Quantification of Peptides and Proteins Using a Standard Curve Approach

    NASA Astrophysics Data System (ADS)

    Greer, Tyler; Lietz, Christopher B.; Xiang, Feng; Li, Lingjun

    2015-01-01

    Absolute quantification of protein targets using liquid chromatography-mass spectrometry (LC-MS) is a key component of candidate biomarker validation. One popular method combines multiple reaction monitoring (MRM) using a triple quadrupole instrument with stable isotope-labeled standards (SIS) for absolute quantification (AQUA). LC-MRM AQUA assays are sensitive and specific, but they are also expensive because of the cost of synthesizing stable isotope peptide standards. While the chemical modification approach using mass differential tags for relative and absolute quantification (mTRAQ) represents a more economical approach when quantifying large numbers of peptides, these reagents are costly and still suffer from lower throughput because only two concentration values per peptide can be obtained in a single LC-MS run. Here, we have developed and applied a set of five novel mass difference reagents, isotopic N, N-dimethyl leucine (iDiLeu). These labels contain an amine reactive group, triazine ester, are cost effective because of their synthetic simplicity, and have increased throughput compared with previous LC-MS quantification methods by allowing construction of a four-point standard curve in one run. iDiLeu-labeled peptides show remarkably similar retention time shifts, slightly lower energy thresholds for higher-energy collisional dissociation (HCD) fragmentation, and high quantification accuracy for trypsin-digested protein samples (median errors <15%). By spiking in an iDiLeu-labeled neuropeptide, allatostatin, into mouse urine matrix, two quantification methods are validated. The first uses one labeled peptide as an internal standard to normalize labeled peptide peak areas across runs (<19% error), whereas the second enables standard curve creation and analyte quantification in one run (<8% error).

  5. The concentration and isotopic composition of osmium in the oceans

    SciTech Connect

    Sharma, M.; Papanastassiou, D.A.; Wasserburg, G.J.

    1997-08-01

    Osmium is one of the rarer elements in seawater. Analytical difficulties have previously prevented the direct measurement of the osmium concentration and isotopic composition in seawater. We report a chemical separation procedure that yields quantitative extraction of osmium standard and of osmium tracer by iron hydroxide precipitation from seawater doped with osmium standard, osmium tracer, and FeCl{sub 3}. The iron hydroxide precipitate is processed to extract osmium, using techniques developed for iron meteorites. Utilizing this procedure, water samples from the Pacific and Atlantic oceans were analyzed for osmium concentration and isotopic composition. Direct determination of the osmium concentration of seawater gives between 15 and 19 fM kg{sup -1}. Detailed experiments on different aliquots of one seawater sample from the North Atlantic Ocean, keeping the amounts of reagents constant, yield concentrations from 16 to 19 fM kg{sup -1}. The variability in concentration is outside the uncertainty introduced because of blanks and indicates a lack of full equilibration between the osmium tracer and seawater osmium. The most reliable osmium concentration of the North Atlantic deep ocean water is 19 fM kg {sup -1} with the {sup 187}Os/{sup 186}Os ratio being 8.7{+-}2 (2{sigma}). Detailed experiments on one seawater sample from the Central Pacific Ocean indicate that the most reliable osmium concentration of the deep ocean water from the Central Pacific is 19 fM kg{sup -1} with the {sup 187}Os/{sup 186}Os ratio being 8.7{+-}0.3 (2{sigma}). The directly measured osmium isotopic composition of the oceans is in good agreement with that obtained from the analysis of some rapidly accumulating organic rich sediments. A sample of ambient seawater around the Juan de Fuca Ridge gave {sup 187}Os/{sup 186}Os = 6.9{+-} 0.4. 42 refs., 6 figs., 4 tabs.

  6. Modeling the carbon isotope composition of bivalve shells (Invited)

    NASA Astrophysics Data System (ADS)

    Romanek, C.

    2010-12-01

    The stable carbon isotope composition of bivalve shells is a valuable archive of paleobiological and paleoenvironmental information. Previous work has shown that the carbon isotope composition of the shell is related to the carbon isotope composition of dissolved inorganic carbon (DIC) in the ambient water in which a bivalve lives, as well as metabolic carbon derived from bivalve respiration. The contribution of metabolic carbon varies among organisms, but it is generally thought to be relatively low (e.g., <10%) in shells from aquatic organism and high (>90%) in the shells from terrestrial organisms. Because metabolic carbon contains significantly more C-12 than DIC, negative excursions from the expected environmental (DIC) signal are interpreted to reflect an increased contribution of metabolic carbon in the shell. This observation contrasts sharply with modeled carbon isotope compositions for shell layers deposited from the inner extrapallial fluid (EPF). Previous studies have shown that growth lines within the inner shell layer of bivalves are produced during periods of anaerobiosis when acidic metabolic byproducts (e.g., succinic acid) are neutralized (or buffered) by shell dissolution. This requires the pH of EPF to decrease below ambient levels (~7.5) until a state of undersaturation is achieved that promotes shell dissolution. This condition may occur when aquatic bivalves are subjected to external stressors originating from ecological (predation) or environmental (exposure to atm; low dissolved oxygen; contaminant release) pressures; normal physiological processes will restore the pH of EPF when the pressure is removed. As a consequence of this process, a temporal window should also exist in EPF at relatively low pH where shell carbonate is deposited at a reduced saturation state and precipitation rate. For example, EPF chemistry should remain slightly supersaturated with respect to aragonite given a drop of one pH unit (6.5), but under closed conditions

  7. The carbon isotopic composition of Novo Urei diamonds

    NASA Technical Reports Server (NTRS)

    Fisenko, A. V.; Semjenova, L. F.; Verchovsky, A. B.; Russell, S. S.; Pillinger, C. T.

    1993-01-01

    The carbon isotopic composition of diamond grains isolated from the Novo Urei meteorite are discussed. A diamond separate was obtained from 2g of whole rock using the chemical treatments described aimed at obtaining very pure diamond. X ray diffraction of the residue, which represented 5000 ppm of the parent mass, indicated only the presence of the desired mineral. The diamond crystals were 1-30 microns in diameter, and some grains had a yellow color. The chemical treatments were followed by a size separation to give a 1-10 microns and a 5-30 microns fraction, which were named DNU-1 and DNU-2, respectively.

  8. Isotopic composition of cosmic-ray boron and nitrogen

    NASA Technical Reports Server (NTRS)

    Krombel, K. E.; Wiedenbeck, M. E.

    1988-01-01

    New measurements of the cosmic-ray boron and nitrogen isotopes at earth and of the elemental abundances of boron, carbon, nitrogen, and oxygen are presented. A region of mutually allowed values for the cosmic-ray nitrogen source ratios is determined, and the cosmic-ray escape mean free path is determined as a function of energy using a leaky box model for cosmic-ray propagation in the Galaxy. Relative to O-16, a N-15 source abundance consistent with solar system composition and a N-14 source abundance which is a factor of about three underabundant relative to the solar value are found.

  9. Easy Absolute Values? Absolutely

    ERIC Educational Resources Information Center

    Taylor, Sharon E.; Mittag, Kathleen Cage

    2015-01-01

    The authors teach a problem-solving course for preservice middle-grades education majors that includes concepts dealing with absolute-value computations, equations, and inequalities. Many of these students like mathematics and plan to teach it, so they are adept at symbolic manipulations. Getting them to think differently about a concept that they…

  10. On the isotopic composition of magmatic carbon in SNC meteorites

    NASA Technical Reports Server (NTRS)

    Wright, I. P.; Grady, M. M.; Pillinger, C. T.

    1992-01-01

    SNC meteorites are thought, from many lines of evidence, to come from Mars. A line of investigation which has been pursued in our laboratory over the years involves measurement of the stable isotopic composition of carbon, in its various forms, in SNC meteorites. In order to establish a firm basis for studying the isotopic systematics of carbon in the martian surface environment, it is first necessary to try and constrain the delta C-13 of bulk Mars. Taking all of the available information, it would seem that the delta C-13 of the Earth's mantle lies somewhere in the range of -5 to -7 percent. Preliminary assessment of magnetic carbon in SNC meteorites, would tend to suggest a delta C-13 of 20 to 30 percent, which is conspicuously different from that of the terrestrial mantle. It is not obvious why there should be such a difference between the two planets, although many explanations are possible. One of these possibilities, that previous delta C-13 measurements for magnetic carbon in SNC meteorites are in error to some degree, is being actively investigated. The most recent results seem to constrain the theta C-13 of the magnetic carbon in SNC meteorites to about -20 percent, which is not at odds with previous estimates. As such, it is considered that a detailed investigation of the carbon isotopic systematics of martian surface materials does have the necessary information with which to proceed.

  11. Microphysical controls on the isotopic composition of wintertime orographic precipitation

    NASA Astrophysics Data System (ADS)

    Moore, M.; Blossey, P. N.; Muhlbauer, A.; Kuang, Z.

    2016-06-01

    The sensitivity of mixed-phase orographic clouds, precipitation, and their isotopic content to changes in dynamics, thermodynamics, and microphysics is explored in idealized two-dimensional flow over a mountain barrier. These simulations use the Weather Research and Forecasting (WRF) model with stable water isotopologues (HDO and H218O), which have been integrated into the Thompson microphysics scheme within WRF as part of the present project. In order to understand how the isotopic composition of precipitation (δ18Oprecip) is fixed, the mountain height, temperature, and the prescribed cloud droplet number concentration (CDNC) have been varied in a series of simulations. For the given range of values explored in this work, changes in mountain height and temperature induce stronger responses in domain-averaged δ18Oprecip than do changes in CDNC by a factor of approximately 10. The strongest response to changing CDNC leads to local variations of δ18Oprecip of about 3‰, though those occur in regions of weak precipitation (<0.1 mm h-1). Changes in δ18Oprecip can be understood through the microphysical pathways by which precipitable hydrometeors are formed and by the isotopic signature associated with each pathway. The decrease in δ18Oprecip with increasing mountain height is not just a function of decreasing temperature but also reflects the changing contributions and distinct isotopic signatures of riming of cloud liquid and vapor deposition onto snow, the leading sources of precipitation in these simulations. The changes in δ18Oprecip with mountain height, temperature, and CDNC are governed in part by the microphysical pathways through which precipitating hydrometeors are formed and grow.

  12. The Li isotopic composition of Oldoinyo Lengai: Nature of the mantle sources and lack of isotopic fractionation during carbonatite petrogenesis

    NASA Astrophysics Data System (ADS)

    Halama, Ralf; McDonough, William F.; Rudnick, Roberta L.; Keller, Jörg; Klaudius, Jurgis

    2007-02-01

    Lithium concentrations and Li isotope compositions are reported for natrocarbonatites and silicate lavas from Oldoinyo Lengai, Tanzania. Natrocarbonatites are characterized by very high Li contents (211-294 ppm) and a narrow range of δ7Li values between + 3.3 and + 5.1. These Li isotope compositions overlap with those reported for MORB and OIB and suggest that the natrocarbonatites reflect the Li isotopic composition of their mantle source. Co-genetic silicate lavas, covering a wide compositional spectrum, show no obvious isotopic fractionation as a function of igneous differentiation or liquid immiscibility. Primitive olivine melilitites (Mg# = 58-70), considered to be parental magmas, contain 14-23 ppm Li and have δ7Li values of + 2.4 to + 4.4. A highly differentiated, peralkaline nephelinite (Mg# = 12), likely to be related to the natrocarbonatites by liquid immiscibility, has about twice as much Li as the melilitite (57 ppm), but a similar isotopic composition (δ7Li = + 3). In contrast, a phonolite with 15 ppm Li has a lighter Li isotope composition (δ7Li = - 0.4), which may reflect assimilation of isotopically light lower crustal mafic granulites, a conclusion supported by radiogenic isotope data. Clinopyroxene and olivine separates from the silicate lavas have uniformly lower Li concentrations (3-15 ppm) and lower δ7Li values (δ7Li = - 2.9 to - 0.5) than the respective whole-rocks, with Δ7Liwhole-rock-mineral between 1.4 and 6.3. This difference between whole-rock and mineral data is interpreted to reflect diffusion-driven isotopic fractionation.

  13. The Abundance and Isotopic Composition of Hg in Extraterrestrial Materials

    NASA Technical Reports Server (NTRS)

    Blum, J. D.; Klaue, Bjorn

    2005-01-01

    During the three year grant period we made excellent progress in our study of the abundances and isotopic compositions of Hg and other volatile trace elements in extraterrestrial materials. At the time the grant started, our collaborating PI, Dante Lauretts, was a postdoctoral research associate working with Peter Buseck at Arizona State University. The work on chondritic Hg was done in collaboration with Dante Lauretta and Peter Buseck and this study was published in Lauretta et a1 (2001a). In July, 2001 Dante Lauretta accepted a position as an Assistant Professor in the Lunar and Planetary Laboratory at the University of Arizona. His funding was transferred and this grant has supported much of his research activities during his first two years at the U of A. Several other papers are in preparation and will be published soon. We presented papers on this topic at Goldschmidt Conferences, the Lunar and Planetary Science Conferences, and the Annual Meetings of the Meteoritical Society. The work done under this grant has spurred several new directions of inquiry, which we are still pursuing. Included in this paper are the studies of bulk abundances and isotopic compositions of metreoritic Mercury, and the development of a thermal analysis ICP-MS technique applied to thermally liable elements.

  14. Genetic Effect on Carbon-Isotope Composition of a Plant

    NASA Astrophysics Data System (ADS)

    Yeh, H.

    2005-05-01

    Stable carbon isotopes of organic sediments are potential tools in investigating a wide spectrum of geological problems. These include paleoclimate, paleoecology, and the origin of life. The quality of the information the tools provides depends largely on our knowledge on the factors determining the isotopic composition of a plant. This is because most biogenic organic sediments are derived from plants. The factors can be grouped into internal and external. The internal factors are ultimately attributable to the genetic make-up of a plant. The most well known internal factor is the photosynthetic pathway. Others include structure of the leave tissue and metabolic characteristics of a plant. External factors are concentration and the isotopic composition of the source CO2 and the physical and chemical conditions of the plant's growth environments. This study addresses primarily the genetic effect, the internal factors. Based on the results of two suites of natural plant samples, it is concluded that the difference in photosynthetic pathway entails about 20.0 % of spread in terms of ä13CPDB values. Genetic effect is also accountable for up to 7.0 to 8.0 % spread in ä13CPDB values within a single category of photosynthetic pathway (i.e. the Calvin cycle). With constrains from the relevant known knowledge, it is concluded that the ä13CPDB values of terrestrial plants are probably ranging from - 8.0 to equal or less than -44.9 %. This range of ä13CPDB values may also be considered the bio-signature of organic sediments of great antiquity.

  15. Lithium Isotopic Composition of the Deep Continental Crust

    NASA Astrophysics Data System (ADS)

    Teng, F.; McDonough, W. F.; Rudnick, R. L.; Gao, S.

    2004-12-01

    We have investigated the Li isotopic composition of the deep continental crust by measuring composite samples from Archean high-grade metamorphic terranes in East China and granulite-facies xenoliths from East China (Hannuoba suite) and Queensland, Australia (Chudleigh and McBride suites). The 30 composite samples, including TTG gneiss, amphibolites and felsic to mafic granulites, have a narrow range of δ 7Li values from +1.7 to +7.5‰ , with an average of +4 ± 1.4‰ (1σ ), which is indistinguishable from the upper mantle. In contrast, the three granulite xenolith suites display a much larger range in δ 7Li, from +15.7 to -17.9‰ with average values decreasing in the order: Hannuoba (-0.7 ± 4.9‰ (1σ , 18 samples)), Chudleigh (-2.5 ± 5.5‰ (1σ , 14 samples)) and McBride (-3.8 ± 7.6‰ (1σ , 12 samples)). The xenoliths are, on average, lighter than the high-grade metamorphic terrane composites. The Li concentrations are also variable with xenoliths having lower Li concentration than high-grade metamorphic terrane composites (5 ± 4 ppm vs. 13 ± 6 ppm, 1σ ). δ 7Li correlates positively with H2O for 12 granulite composites; mafic samples have the highest H2O contents and δ 7Li values while felsic ones have the lowest. This, together with an excellent positive correlation between Li concentration and Mg# for 13 TTG gneiss composites, suggests that both metamorphic dehydration and protolith lithology play important roles in determining the Li isotopic composition of metamorphic rocks. For the Hannuoba xenoliths, δ 7Li correlates positively with Al2O3/CaO and negatively with Li, FeO, MgO, CaO and Co, suggesting that the protolith composition primarily controls the δ 7Li values. No such correlations are found for the other granulite xenoliths. The difference in δ 7Li between terranes and granulite xenoliths may reflect evolving lighter δ 7Li with depth in the crust, since the former equilibrated at middle to upper lower crustal depths, while the

  16. The chlorine isotopic composition of Martian meteorites 1: Chlorine isotope composition of Martian mantle and crustal reservoirs and their interactions

    NASA Astrophysics Data System (ADS)

    Williams, J. T.; Shearer, C. K.; Sharp, Z. D.; Burger, P. V.; McCubbin, F. M.; Santos, A. R.; Agee, C. B.; McKeegan, K. D.

    2016-05-01

    The Martian meteorites record a wide diversity of environments, processes, and ages. Much work has been done to decipher potential mantle sources for Martian magmas and their interactions with crustal and surface environments. Chlorine isotopes provide a unique opportunity to assess interactions between Martian mantle-derived magmas and the crust. We have measured the Cl-isotopic composition of 17 samples that span the range of known ages, Martian environments, and mantle reservoirs. The 37Cl of the Martian mantle, as represented by the olivine-phyric shergottites, NWA 2737 (chassignite), and Shergotty (basaltic shergottite), has a low value of approximately -3.8‰. This value is lower than that of all other planetary bodies measured thus far. The Martian crust, as represented by regolith breccia NWA 7034, is variably enriched in the heavy isotope of Cl. This enrichment is reflective of preferential loss of 35Cl to space. Most basaltic shergottites (less Shergotty), nakhlites, Chassigny, and Allan Hills 84001 lie on a continuum between the Martian mantle and crust. This intermediate range is explained by mechanical mixing through impact, fluid interaction, and assimilation-fractional crystallization.

  17. Perchlorate in The Great Lakes: Distribution, Isotopic Composition and Origin

    NASA Astrophysics Data System (ADS)

    Poghosyan, A.; Sturchio, N. C.; Jackson, W. A.; Guan, Y.; Eiler, J. M.; Hatzinger, P. B.

    2013-12-01

    Concentrations, stable chlorine and oxygen isotopic compositions, and 36Cl abundances of perchlorate were investigated in the five Laurentian Great Lakes. Samples were collected during monitoring cruises in 2007 and 2008 of the U.S. EPA's RV Lake Guardian and in 2010 at the water supply intake of Marquette, MI on the southern shore of Lake Superior. Concentrations of perchlorate were measured by IC/MS/MS at 24 locations, including one or two depth profiles in each lake. Mean concentrations (μg/L) are: Superior, 0.06 × 0.01; Michigan, 0.10 × 0.01; Huron, 0.11 × 0.01; Erie, 0.08 × 0.01, and Ontario, 0.09 × 0.01. Concentration vs. depth is nearly constant in each lake, indicating well-mixed conditions. Perchlorate was extracted from near-surface water by passing 15,000 to 80,000 L of water through 1-L cartridges containing Purolite A530E bifunctional anion-exchange resin. In the laboratory, perchlorate was eluted from the resin, purified, and precipitated as a >99% pure crystalline phase. Milligram amounts were recovered from each lake. Chlorine and oxygen isotopic analyses were performed at Caltech using the Cameca 7f-GEO SIMS instrument, following validation of the SIMS method with analyses of USGS-37 and USGS-38 isotopic reference materials. Results indicate a relatively narrow range in δ37Cl values (+2.9 to +3.9 ‰) and a wider range in δ18O values (-4.0 to +4.1 ‰), with a general geographic trend of increasing δ18O from west to east. Oxygen-17 was measured at UIC using dual-inlet IRMS of O2 produced by decomposition of KClO4. Great Lakes perchlorate has mass-independent oxygen isotopic variations with positive Δ17O values (+1.6 ‰ to +2.7 ‰) divided into two distinct groups: Lake Superior (+2.7 ‰) and the other four lakes (~ +1.7 ‰). The isotopic data indicate that perchlorate is dominantly of natural origin, having stable isotopic compositions resembling those of perchlorate from pre-industrial groundwaters in the western USA. The 36Cl

  18. Continuous measurements of isotopic composition of water vapour on the East Antarctic Plateau

    NASA Astrophysics Data System (ADS)

    Casado, Mathieu; Landais, Amaelle; Masson-Delmotte, Valérie; Genthon, Christophe; Kerstel, Erik; Kassi, Samir; Arnaud, Laurent; Picard, Ghislain; Prie, Frederic; Cattani, Olivier; Steen-Larsen, Hans-Christian; Vignon, Etienne; Cermak, Peter

    2016-07-01

    Water stable isotopes in central Antarctic ice cores are critical to quantify past temperature changes. Accurate temperature reconstructions require one to understand the processes controlling surface snow isotopic composition. Isotopic fractionation processes occurring in the atmosphere and controlling snowfall isotopic composition are well understood theoretically and implemented in atmospheric models. However, post-deposition processes are poorly documented and understood. To quantitatively interpret the isotopic composition of water archived in ice cores, it is thus essential to study the continuum between surface water vapour, precipitation, surface snow and buried snow. Here, we target the isotopic composition of water vapour at Concordia Station, where the oldest EPICA Dome C ice cores have been retrieved. While snowfall and surface snow sampling is routinely performed, accurate measurements of surface water vapour are challenging in such cold and dry conditions. New developments in infrared spectroscopy enable now the measurement of isotopic composition in water vapour traces. Two infrared spectrometers have been deployed at Concordia, allowing continuous, in situ measurements for 1 month in December 2014-January 2015. Comparison of the results from infrared spectroscopy with laboratory measurements of discrete samples trapped using cryogenic sampling validates the relevance of the method to measure isotopic composition in dry conditions. We observe very large diurnal cycles in isotopic composition well correlated with temperature diurnal cycles. Identification of different behaviours of isotopic composition in the water vapour associated with turbulent or stratified regime indicates a strong impact of meteorological processes in local vapour/snow interaction. Even if the vapour isotopic composition seems to be, at least part of the time, at equilibrium with the local snow, the slope of δD against δ18O prevents us from identifying a unique origin leading

  19. Investigation of magnesium isotope fractionation during granite differentiation: Implication for Mg isotopic composition of the continental crust

    NASA Astrophysics Data System (ADS)

    Liu, Sheng-Ao; Teng, Fang-Zhen; He, Yongsheng; Ke, Shan; Li, Shuguang

    2010-09-01

    High-precision Mg isotopic analysis was performed on a suite of well-characterized I-type granitoids and associated hornblende and biotite minerals from the Dabie Orogen in central China, to address the behavior of Mg isotopes during granite differentiation. Although these granitoids formed through different degrees of partial melting and fractional crystallization, with large variations in elemental and mineral compositions, their δ26Mg values vary from -0.26 to -0.14 and are indistinguishable within our analytical precision (± 0.07‰; 2 SD). Coexisting hornblendes and biotites in these granitoids display similar Mg isotopic composition, with δ26Mg ranging from -0.31 to -0.14 in hornblendes and -0.23 to -0.12 in biotites. The inter-mineral fractionation factors (Δ 26Mg Hbl-Bt = δ26Mg Hbl - δ26Mg Bt) vary from -0.10 to -0.02, with an average = -0.06 ± 0.08 (2 SD). The limited inter-mineral fractionation agrees with the theoretic prediction that Mg cations in both hornblende and biotite are octahedrally coordinated with oxygen, which restricts the magnitude of equilibrium isotope fractionation. Overall, data from both bulk granitoids and associated mineral separates suggest that Mg isotope fractionation during I-type granite differentiation is limited. Collectively, granitoids studied here have Mg isotopic composition similar to that of terrestrial basalts and peridotites ( δ26Mg = -0.21 ± 0.07 vs. -0.25 ± 0.07; 2 SD), confirming that magmatic processes do not significantly fractionate Mg isotopes. The continental crust in the Dabie Orogen, as sampled by these I-type granitoids, has a mantle-like Mg isotopic composition. Given that significant Mg isotope fractionation occurs during chemical weathering processes, Mg isotopes may potentially be used for tracing granite genesis, in particular, if sedimentary materials are involved in granite sources.

  20. Reformulated 17O correction of mass spectrometric stable isotope measurements in carbon dioxide and a critical appraisal of historic 'absolute' carbon and oxygen isotope ratios

    NASA Astrophysics Data System (ADS)

    Kaiser, Jan

    2008-03-01

    Mass-spectrometric stable isotope measurements of CO 2 use molecular ion currents at mass-to-charge ratios m/ z 44, 45 and 46 to derive the elemental isotope ratios n( 13C)/ n( 12C) and n( 18O)/ n( 16O), abbreviated 13C/ 12C and 18O/ 16O, relative to a reference. The ion currents have to be corrected for the contribution of 17O-bearing isotopologues, the so-called ' 17O correction'. The magnitude of this correction depends on the calibrated isotope ratios of the reference. Isotope ratio calibrations are difficult and are therefore a matter of debate. Here, I provide a comprehensive evaluation of the existing 13C/ 12C ( 13R), 17O/ 16O ( 17R) and 18O/ 16O ( 18R) calibrations of the reference material Vienna Standard Mean Ocean Water (VSMOW) and CO 2 generated from the reference material Vienna Pee Dee Belemnite (VPDB) by reaction with 100% H 3PO 4 at 25 °C (VPDB-CO 2). I find 17R/10-6=382.7-2.1+1.7, 18RVSMOW/10 -6 = 2005.20 ± 0.45, 13R/10-6= 11124 ± 45, 17R/10-6=391.1-2.1+1.7 and 18R/10-6=2088.37±0.90. I also rephrase the calculation scheme for the 17O correction completely in terms of relative isotope ratio differences ( δ values). This reveals that only ratios of isotope ratios (namely, 17R/ 13R and 13R17R/ 18R) are required for the 17O correction. These can be, and have been, measured on conventional stable isotope mass spectrometers. I then show that the remaining error for these ratios of isotope ratios can lead to significant uncertainty in the derived relative 13C/ 12C difference, but not for 18O/ 16O. Even though inter-laboratory differences can be corrected for by a common 'ratio assumption set' and/or normalisation, the ultimate accuracy of the 17O correction is hereby limited. Errors of similar magnitude can be introduced by the assumed mass-dependent relationship between 17O/ 16O and 18O/ 16O isotope ratios. For highest accuracy in the 13C/ 12C ratio, independent triple oxygen isotope measurements are required. Finally, I propose an experiment that

  1. Evaluating Foraminifera as an Archive for Seawater Chromium Isotopic Composition

    NASA Astrophysics Data System (ADS)

    Wang, X.; Planavsky, N.; Hull, P. M.; Tripati, A.; Reinhard, C.; Zou, H.; Elder, L. E.; Henehan, M. J.

    2015-12-01

    In recent years there has been growing interest in using chromium isotopes (δ53Cr) as a proxy to investigate the redox evolution of Earth's ocean-atmosphere system throughout geological history. Potential archives for seawater δ53Cr that have been identified to date include iron formations and organic-rich siliciclastic sediments. However, these types of sediments are not common and they are discontinuous over geologic time. As a result, alternative types of archives are needed. Here we evaluate the utility of foraminifera tests as a recorder of seawater δ53Cr. Core-tops used were from different ocean basins. Mono-specific samples of Globigerinoides sacculifer, Orbulina universa, Pulleniatina obliquiloculata, Globoratalia crassula-crassaformis, Globoratalia truncatulinoides, and Globigerinella siphonifera were isolated to investigate inter-species isotope fractionation. Chromium concentrations were measured by isotope dilution method to be 0.1-0.3 μg/g. The δ53Cr values of these species range from 0.2‰ to 2.4‰, with an analytical uncertainty of 0.3‰ (95% confidence). Despite the high analytical uncertainty due to the extremely low levels of Cr present, there is still large detectable variation in foraminiferal δ53Cr values, which overlap presently available seawater values (Bonnand et al., 2013; Scheiderich et al., 2015). Possible explanations for such variations in foraminiferal δ53Cr values include heterogeneity of seawater δ53Cr in the modern oceans, and/or photobiochemical redox cycling of Cr in the surface oceans. Therefore, care should be taken when using foraminifera to reconstruct past seawater δ53Cr values. ReferencesBonnand, P., James, R., Parkinson, I., Connelly, D., Fairchild, I., 2013. The chromium isotopic composition of seawater and marine carbonates. Earth and Planetary Science Letters, 382: 10-20. Scheiderich, K., Amini, M., Holmden, C., Francois, R., 2015. Global variability of chromium isotopes in seawater demonstrated by Pacific

  2. Amino acid nitrogen isotopic composition patterns in lacustrine sedimenting matter

    NASA Astrophysics Data System (ADS)

    Carstens, Dörte; Lehmann, Moritz F.; Hofstetter, Thomas B.; Schubert, Carsten J.

    2013-11-01

    Amino acids (AAs) comprise a large fraction of organic nitrogen (N) in plankton and sedimenting matter. Aquatic studies of organic N compounds in general and of AAs in particular, mostly concentrate on marine environments. In order to study the cycling and fate of organic N and AAs in lakes, we measured the N isotopic composition (δ15N) of bulk organic matter (OM) and of single hydrolysable AAs in sediment trap and sediment samples from two Swiss lakes with contrasting trophic state: Lake Brienz, an oligotrophic lake with an oxic water column, and Lake Zug a eutrophic, meromictic lake. We also measured the N isotopic composition of water column nitrate, the likely inorganic N source during biosynthesis in both lakes. The δ15N-AA patterns found for the sediment trap material were consistent with published δ15N-AA data for marine plankton. The AA composition and primary δ15N-AA signatures are preserved until burial in the sediments. During early sedimentary diagenesis, the δ15N values of single AAs appear to increase, exceeding those of the bulk OM. This increase in δ15N-AA is paralleled by a decreased contribution of AAs to the total OM pool with progressed degradation, suggesting preferential AA degradation associated with a significant N isotope fractionation. Indicators for trophic level based on δ15N-AAs were determined, for the first time in lacustrine systems. In our samples, the trophic AAs were generally enriched in 15N compared to source AAs and higher trophic δ15N-AA values in Lake Zug were consistent with a higher trophic level of the bulk biomass compared to Lake Brienz. Especially the difference between average trophic δ15N-AAs and average source δ15N-AAs was sensitive to the trophic states of the two lakes. A proxy for total heterotrophic AA re-synthesis (ΣV), which is strongly associated with heterotrophic microbial reworking of the OM, was calculated based on δ15N values of trophic AAs. Higher ΣV in Lake Brienz indicate enhanced

  3. Triple sulfur isotope composition of Late Archean seawater sulfate

    NASA Astrophysics Data System (ADS)

    Paris, G.; Fischer, W. W.; Sessions, A. L.; Adkins, J. F.

    2013-12-01

    Multiple sulfur isotope ratios in Archean sedimentary rocks have provided powerful insights into the behavior of the ancient sulfur cycle, the redox state of fluid Earth, and the timing of the rise of atmospheric oxygen [1]. Most processes fractionate sulfur isotopes in proportion to their mass differences, but the Archean sulfur isotope record is marked by pronounced mass-independent fractionation (MIF, Δ33S≠0). The origin of these signatures has been traditionally interpreted as the result of photolysis of SO2 from short wavelength UV light, with positive Δ33S values recorded in pyrite and negative Δ33S values in sulfate-bearing phases [2]. This long-held hypothesis rests on observations of negative Δ33S from enigmatic barite occurrences from mixed volcanic sedimentary strata in Mesoarchean greenstone terrains. Despite forming the framework for understanding Archean sulfur cycle processes [3], it is largely untested [3]. It is largely untested. Consequently, the biggest challenge to our current understanding of the early sulfur cycle is a poor understanding of the isotopic composition of seawater sulfate. Sulfate evaporite minerals are absent from Archean strata and the sulfur isotope record is written entirely by measurements of pyrite. Carbonate associated sulfate (CAS) provides an important archive for assaying the isotopic composition of ancient seawater sulfate It has been exploited in many studies of Phanerozoic and Proterozoic sulfate but have been only marginally used thus far for Archean samples because of the extremely low concentration of CAS in limestones and dolomites from this era. We have developed a novel MC-ICP-MS approach to solve this problem [4]. This new method lowers the detection limit by up to three orders of magnitude for δ34S and Δ33S measurements, enabling to work on a few nmols of sulfate which represent only tens of mg of sample powders micromilled from specific carbonate textures. Two stratigraphic sections from the 2

  4. Development and validation of a single collector ICPMS procedure to determine boron isotopeic compositions of water and food samples

    NASA Astrophysics Data System (ADS)

    Vogl, Jochen; Rosner, Martin; Pritzkow, Wolfgang

    2010-05-01

    Authenticity and provenance studies as well as issues in environmental- and geo-sciences are hot topics in nowadays isotope research. Elements being known for their natural isotopic variation, such as lead and strontium, are being used to assign the provenance of artefacts, food and other products. A recent study revealed the potential of boron (B) isotopes for delivering information on the provenance of crop plants. To offer alternative analytical instrumentations beside the classical TIMS procedures a single collector ICPMS procedure for B isotope analyses has been developed and validated. This procedure should enable more B isotope studies, as single collector ICPMS intruments are more widepread in the relevant laboratories compared to TIMS. The developed procedures for the determination of B isotopic compositions use a magnetic sector ICPMS and consist of one low resolution (LR) and one medium resolution (MR) procedure. The absolute standard deviation for the δ11B determination in three independently measured samples lies between 0.2 and 0.8 ‰ for the LR and between 0.3 and 1.5 ‰ for the MR. The expanded uncertainties with a coverage factor of k=2 range between 1.4 and 1.6 ‰ for the LR and between 2.9 and 3.2 ‰ for the MR. The trueness, expressed as average deviation from the reference values, is less than 1.1 ‰ for LR and 0.8 ‰ for MR. To test the practicability of the procedure the matrix tolerance has been investigated. Using a measurement solution containing 100 µg/kg boron a matrix of 2 mg/kg of alkaline and earth alkaline elements was found as a limit for stable instrumental mass discrimination. Thus a highly efficient matrix separation is required, similar to TIMS. The developed procedure is well suited for the for B isotope studies of various matrices and especially the LR procedure offers relatively small uncertainties combined with high sample throughput.

  5. Trace element and oxygen isotope composition of Hawaiian hotspot zircon

    NASA Astrophysics Data System (ADS)

    Vazquez, J. A.; Bindeman, I. N.; Shamberger, P. J.; Hammer, J. E.

    2010-12-01

    The trace element and isotopic compositions of zircon are increasingly used to delimit the provenance of detrital minerals in sedimentary rocks, as well as the dynamics and timescales of magmagenesis and metamorphism. Numerous studies document the characteristics of zircon hosted by continental and MORB-related rocks, but the characteristics of zircon generated in magmas from oceanic hotspots are relatively unknown. We present the trace element and O-isotope compositions of Hawaiian zircon from gabbroic and dioritic xenoliths sampled by Holocene basalts at Hualalai volcano. The plutonic zircon yield U-Pb and 238U-230Th ages of ca. 250 ka and 40 ka and grew from intrusions of highly fractionated alkalic magma lodged at >10 km depths (Shamberger & Hammer, 2006; Vazquez et al., 2007). Individual Hualalai zircon are euhedral to anhedral with inclusions of feldspars, pyroxenes, and trachytic glass. Zoning apparent in cathodoluminescence images is generally indistinct, but a significant minority of crystals has rims with relatively high luminescence. Ion microprobe analyses of individual zircon crystals reveal trace element zoning that generally correlates with luminescence. Up to 20-fold variation in HREE concentrations, with overall positive correlation between Eu/Eu* and Ti and inverse correlation between Hf and Ti, characterize Hualalai zircon. These relations are similar to those reported for zircon from some felsic suites related by cooling-induced fractionation. Luminescent rims have relatively low REE, Hf, and Y, but have Ti concentrations like their corresponding interiors. Ti-in-zircon thermometry yields temperatures between 800-1000°C after adjustments for sub-unity TiO2 and SiO2 activities using silicate-oxide equilibria. These temperatures are generally consistent with temperatures derived from two-feldspar and glass-pyroxene pairs included by single zircon crystals. Despite compositional differences, zircon interiors and luminescent rims yield 238U-230Th

  6. Variations in Urine Calcium Isotope: Composition Reflect Changes in Bone Mineral Balance in Humans

    NASA Technical Reports Server (NTRS)

    Skulan, Joseph; Anbar, Ariel; Bullen, Thomas; Puzas, J. Edward; Shackelford, Linda; Smith, Scott M.

    2004-01-01

    Changes in bone mineral balance cause rapid and systematic changes in the calcium isotope composition of human urine. Urine from subjects in a 17 week bed rest study was analyzed for calcium isotopic composition. Comparison of isotopic data with measurements of bone mineral density and metabolic markers of bone metabolism indicates the calcium isotope composition of urine reflects changes in bone mineral balance. Urine calcium isotope composition probably is affected by both bone metabolism and renal processes. Calcium isotope. analysis of urine and other tissues may provide information on bone mineral balance that is in important respects better than that available from other techniques, and illustrates the usefulness of applying geochemical techniques to biomedical problems.

  7. Chemistry and isotopic composition of fumarole discharges of Furnas caldera

    NASA Astrophysics Data System (ADS)

    Ferreira, Teresa; Oskarsson, Niels

    1999-09-01

    Two fumarole grounds at Lagoa das Furnas and Furnas village and a fumarole on the bank of Ribeira dos Tambores are located on a west-east tectonic lineament across the topographic low of the Furnas caldera. The discharge of the fumaroles derives from steam separation from shallow (100-200 m) aquifers at temperatures of about 180°C. As inferred from nitrogen/argon relations and deuterium-oxygen isotope relations the hydrothermal fluid is derived from local precipitation after some 10% steam fractionation in the fumarole conduits. Sulphur isotope ratios of the discharge, being close to those of juvenile rock sulphur, indicate extensive rock-leaching within the aquifers. The carbon isotope composition of the fumarole discharge and carbon dioxide saturated waters encountered across the caldera floor suggests that the source of carbon is regional outgassing of mantle derived juvenile carbon dioxide. Chemistry of the acid gases, carbon dioxide and hydrogen sulphide in the discharge indicates a slight fractionation induced by different boiling in the shallow hydrothermal aquifers. Traces of hydrogen and methane contained in the discharge bear no relation to the low temperature water-steam equilibria of the Furnas fumaroles. Assuming a deeper origin of these gases, a simple model for binary mixtures of methane and hydrogen indicates that these gases are derived from supercritical conditions, presumably equilibrated within hot rocks below the hydrothermal system. The remarkably stable ratios of hydrogen and methane, also considering their inferred deep origin, suggest that these gases might be considered for future chemical monitoring of the fumarole discharge in Furnas.

  8. Isotopic composition of sulfate accumulations, Northern Calcareous Alps, Austria

    NASA Astrophysics Data System (ADS)

    Bojar, Ana-Voica; Halas, Stanislaw; Bojar, Hans-Peter; Trembaczowski, Andrzej

    2015-04-01

    The Eastern Alps are characterised by the presence of three main tectonic units, such as the Lower, Middle and Upper Austroalpine, which overlie the Penninicum (Tollmann, 1977). The Upper Austroalpine unit consists of the Northern Calcareous Alps (NCA) overlying the Greywacke zone and corresponding to the Graz Paleozoic, Murau Paleozoic and the Gurktal Nappe. Evaporitic rocks are lacking in the later ones. The Northern Calcareous Alps are a detached fold and thrust belt. The sedimentation started in the Late Carboniferous or Early Permian, the age of the youngest sediments being Eocene. The NCA are divided into the Bajuvaric, Tirolic and Juvavic nappe complexes. The evaporitic Haselgebirge Formation occurs in connection with the Juvavic nappe complex at the base of the Tirolic units (Leitner et al., 2013). The Haselgebirge Formation consists mainly of salt, shales, gypsum and anhydrite and includes the oldest sediments of the NCA. The age of the Haselgebirge Formation, established by using spors and geochronological data, is Permian to Lower Triassic. For the Northern Calcareous Alps, the mineralogy of sulphate accumulations consists mainly of gypsum and anhydrite and subordonates of carbonates. The carbonates as magnesite, dolomite and calcite can be found either as singular crystals or as small accumulations within the hosting gypsum. Sulfides (sphalerite, galena, pyrite), sulfarsenides (enargite, baumhauerite) and native sulphur enrichments are known from several deposits (Kirchner, 1987; Postl, 1990). The investigated samples were selected from various gypsum and halite rich deposits of the Northern Calcareous Alps. A total of over 20 samples were investigated, and both oxygen and sulfur isotopic composition were determined for anhydrite, gyps, polyhalite, blödite and langbeinite. The sulfur isotopic values vary between 10.1 to 14 ‰ (CDT), with three values higher than 14 ‰. The Oxygen isotopic values show a range from 9 to 23 ‰ (SMOW). The sulfur

  9. Morphology-Composition-Isotopes: Recent Results from Observations

    NASA Astrophysics Data System (ADS)

    Schulz, R.

    This article presents some recent imaging and spectroscopic observations that led to results which are significant for understanding the properties of comet nuclei. The coma morphology and/or composition were investigated for 12 comets belonging to different dynamical classes. The data analysis showed that the coma morphology of three non-periodic comets is not consistent with the general assumption that dynamically new comets still have a relatively uniform nucleus surface and therefore do not exhibit gas and/or dust jets in their coma. The determination of carbon and nitrogen isotopic ratios revealed the same values for all comets investigated at various heliocentric distances. However, the relative abundance of the rare nitrogen isotope 15N is about twice as high as in the Earth's atmosphere. Observations of comets at splitting events and during outbursts led to indications for differences between material from the nucleus surface and the interior. The monitoring of the induced outburst of 9P/Temple revealed that under non-steady state conditions the fast disintegration of species is detectable.

  10. Lithium isotope fractionation in the Ganges-Brahmaputra floodplain and implications for groundwater impact on seawater isotopic composition

    NASA Astrophysics Data System (ADS)

    Bagard, Marie-Laure; West, A. Joshua; Newman, Karla; Basu, Asish R.

    2015-12-01

    Lithium isotopes are a promising proxy for reconstructing past weathering processes, but unraveling the seawater record requires a comprehensive understanding of the magnitude and isotopic composition of Li fluxes to the oceans, and of how these change over time. Little information is available on the role of floodplain sediments and groundwater systems in setting the Li isotope signature of the dissolved flux delivered from the continents to the oceans. Here we investigate the Li dissolved fluxes of river waters and groundwaters in the Ganges-Brahmaputra floodplain. The data suggest that a maximum of 3.1 ×108 and 1.5 ×108 moles Li/yr are carried to the Bay of Bengal by Ganges-Brahmaputra rivers and groundwaters, respectively. The riverine flux has a significantly heavier Li isotope composition (average δ7Li: 26‰) than the groundwater flux (average δ7Li: 16‰) and increases downstream across the floodplain. δ7Li in both river waters and shallow groundwater can be explained by Li scavenging by Quaternary floodplain sediments following a Rayleigh fractionation process, with preferential removal of 6Li. On the other hand, deep groundwaters (>40 m) contributing to submarine groundwater discharge to the Bay of Bengal are enriched in 6Li at depth, likely due to the dissolution of floodplain sediments releasing Li with a light isotope composition. Similarly low δ7Li has been reported in other large sedimentary aquifers. The deep groundwater values are close to the average isotope composition of the global Li inputs to the ocean (∼15‰), so groundwater submarine discharge has only a minor influence on the assessment of the modern Li isotope budget of the ocean. Our analysis further suggests that groundwater discharge of Li has probably played at most a small and secondary role in past changes in the isotope composition of the total continental flux of Li to the ocean.

  11. Carbon and hydrogen isotopic compositions of stratospheric methane: 2. Two-dimensional model results and implications for kinetic isotope effects

    NASA Astrophysics Data System (ADS)

    McCarthy, M. C.; Boering, K. A.; Rice, A. L.; Tyler, S. C.; Connell, P.; Atlas, E.

    2003-08-01

    New high-precision measurements of the carbon and hydrogen isotopic compositions of stratospheric CH4 made on whole air samples collected aboard the NASA ER-2 aircraft are compared with results from the Lawrence Livermore National Laboratory 2-D model. Model runs incorporating sets of experimentally determined kinetic isotope effects (KIEs) for the reactions of CH4 with each of the oxidants OH, O(1D), and Cl are examined with the goals of determining (1) how well the 2-D model can reproduce the observations for both the carbon and hydrogen isotopic compositions, (2) what factors are responsible for the observed increase in the apparent isotopic fractionation factors with decreasing methane mixing ratios, and (3) how sensitive the modeled isotopic compositions are to various experimentally determined KIEs. Bound by estimates of the effects of uncertainties in model chemistry and transport on isotopic compositions, we then examine the constraints the ER-2 observations place on values for the KIEs. For the carbon KIE for reaction of CH4 with O(1D), for example, the analysis of model results and observations favors the larger of the experimental values, 1.013, over a value of 1.001. These analyses also suggest that intercomparisons of results from different models using a given set of KIEs may be useful as a new diagnostic of model-model differences in integrated chemistry and transport.

  12. Chemical composition of HAL, an isotopically-unusual Allende inclusion

    NASA Technical Reports Server (NTRS)

    Davis, A. M.; Tanaka, T.; Grossman, L.; Lee, T.; Wasserburg, G. J.

    1982-01-01

    Samples of hibonite, black rim, and portions of friable rim from an unusual Allende inclusion, named HAL, were analyzed by INAA and RNAA for 37 major, minor, and trace elements. An unusually low amount of Ce was found in HAL, although it otherwise was highly enriched in REE compared to C1 chondrites. HAL is also depleted in Sr, Ba, U, V, Ru, Os, and Ir relative to other refractory elements. It is concluded that the distribution of REE between hibonite and rims was established when hibonite and other refractory minerals were removed at slightly different temperatures from a hot, oxidizing gas in which they previously coexisted as separate grains. Possible locations for the chemical and mass dependent isotopic fractionation are considered to be in ejecta from the low temperature helium-burning zone of a supernova and in the locally oxidizing environment generated by evaporation of interstellar grains of near-chondritic chemical composition.

  13. The elemental and isotopic composition of galactic cosmic ray nuclei

    NASA Technical Reports Server (NTRS)

    Mewaldt, R. A.

    1983-01-01

    A directly accessible sample of matter which originates outside the solar system is provided by galactic cosmic rays. The present investigation is primarily concerned with progress related to questions raised regarding the similarity or difference between solar system matter and matter coming from outside the solar system. The investigation takes into account U.S. contributions to this topic over the period from 1979 to 1982. The cosmic ray (CR) abundances of all the elements from H to Ni (atomic number Z=1 to 28) have now been measured. Cosmic ray source (CRS) and solar system (SS) elemental compositions are listed in a table, and the ratio of CRS to SS abundance for 21 elements is shown in a graph. There is now clear evidence from CR isotope studies that the nucleosynthesis of CRS material has differed from that of SS material.

  14. Neodymium isotope evidence for a chondritic composition of the Moon.

    PubMed

    Rankenburg, K; Brandon, A D; Neal, C R

    2006-06-01

    Samarium-neodymium isotope data for six lunar basalts show that the bulk Moon has a 142Nd/144Nd ratio that is indistinguishable from that of chondritic meteorites but is 20 parts per million less than most samples from Earth. The Sm/Nd formation interval of the lunar mantle from these data is 215(-21)(+23) million years after the onset of solar system condensation. Because both Earth and the Moon likely formed in the same region of the solar nebula, Earth should also have a chondritic bulk composition. In order to mass balance the Nd budget, these constraints require that a complementary reservoir with a lower 142Nd/144Nd value resides in Earth's mantle. PMID:16741118

  15. Probing the Crystal Structure, Composition-Dependent Absolute Energy Levels, and Electrocatalytic Properties of Silver Indium Sulfide Nanostructures.

    PubMed

    Saji, Pintu; Ganguli, Ashok K; Bhat, Mohsin A; Ingole, Pravin P

    2016-04-18

    The absolute electronic energy levels in silver indium sulfide (AIS) nanocrystals (NCs) with varying compositions and crystallographic phases have been determined by using cyclic voltammetry. Different crystallographic phases, that is, metastable cubic, orthorhombic, monoclinic, and a mixture of cubic and orthorhombic AIS NCs, were studied. The band gap values estimated from the cyclic voltammetry measurements match well with the band gap values calculated from the diffuse reflectance spectra measurements. The AIS nanostructures were found to show good electrocatalytic activity towards the hydrogen evolution reaction (HER). Our results clearly establish that the electronic and electrocatalytic properties of AIS NCs are strongly sensitive to the composition and crystal structure of AIS NCs. Monoclinic AIS was found to be the most active HER electrocatalyst, with electrocatalytic activity that is almost comparable to the MoS2 -based nanostructures reported in the literature, whereas cubic AIS was observed to be the least active of the studied crystallographic phases and compositions. In view of the HER activity and electronic band structure parameters observed herein, we hypothesize that the Fermi energy level of AIS NCs is an important factor that decides the electrocatalytic efficiency of these nanocomposites. The work presented herein, in addition to being the first of its kind regarding the composition and phase-dependence of electrochemical aspects of AIS NCs, also presents a simple solvothermal method for the synthesis of different crystallographic phases with various Ag/In molar ratios. PMID:26812447

  16. Application of Pb isotopes to the absolute timing of regional exposure events in carbonate rocks: An example from U-rich dolostones from the Wahoo Formation (Pennsylvanian), Prudhoe Bay, Alaska

    SciTech Connect

    Hoff, J.A.; Hanson, G.N.; Jameson, J.

    1995-01-02

    Pb isotope data from U-rich dolostones from the Wahoo Formation (Pennsylvanian) from the subsurface at Prudhoe Bay, alaska, demonstrate that the U-Th-Pb system can be a powerful geochemical and geochronological tool in understanding carbonate diagenesis. These U-rich dolostones are developed beneath a major, Late Permian to Early Triassic truncational unconformity. U enrichment is uniquely associated with the mineral dolomite, but anomalously high concentrations of U are not present within the dolomite crystal lattice. Major mineral or fluid phases can be ruled out as U hosts. SEM analyses indicate that U anomalies are present in an unknown mineral phase associated with authigenic clays and are commonly concentrated along stylolites. Geologic, petrographic, and geochemical data indicate that the bulk of dolomitization occurred during the Permo-Triassic, following development of a regional unconformity (Jameson 1989a, 1989b, 1990a, 1990b, 1994). In this study, the Pb isotopic composition of these U-rich dolostones is used to establish the absolute timing of U enrichment and its relationship to dolomitization and to the burial history of the Wahoo Formation.

  17. The silicon isotopic composition of the Ganges and its tributaries

    NASA Astrophysics Data System (ADS)

    Fontorbe, Guillaume; De La Rocha, Christina L.; Chapman, Hazel J.; Bickle, Michael J.

    2013-11-01

    The silicon isotopic composition (δSi30) of the headwaters of the Ganges River, in the Himalaya, ranged from +0.49±0.01‰ to +2.17±0.04‰ at dissolved silicon (DSi) concentrations of 38 to 239 μM. Both the concentration and isotopic composition of DSi in the tributaries increased between the highest elevations to where the Ganges leaves the Himalayas at Rishikesh. The tributaries exhibit a linear correlation between δSi30 and DSi that may represent mixing between a low DSi, low δSi30 (e.g., 40 μM, +0.5‰) component potentially reflecting fractionation during adsorption of a small fraction of silicon onto iron oxides and a high DSi, high δSi30 component (e.g., 240 μM, +1.7‰) produced during higher intensity weathering with a greater proportional sequestration of weathered silicon into secondary minerals or biogenic silica. On the Ganges alluvial plain, in the Ganges and the Yamuna, Gomati, and their tributaries, DSi ranged from 122 to 218 μM while δSi30 ranged from +1.03±0.03‰ to +2.46±0.06‰. Highest values of δSi30 occurred in the Gomati and its tributaries. In general, the lower DSi and higher δSi30 of DSi in these rivers suggests control of both by removal of DSi by secondary mineral formation and/or biogenic silica production. A simple 1-dimensional model with flow through a porous medium is introduced and provides a useful framework for understanding these results.

  18. Baseline shifts in coral skeletal oxygen isotopic composition: a signature of symbiont shuffling?

    NASA Astrophysics Data System (ADS)

    Carilli, J. E.; Charles, C. D.; Garren, M.; McField, M.; Norris, R. D.

    2013-06-01

    Decades-long records of the stable isotopic composition of coral skeletal cores were analyzed from four sites on the Mesoamerican Reef. Two of the sites exhibited baseline shifts in oxygen isotopic composition after known coral bleaching events. Changes in pH at the calcification site caused by a change in the associated symbiont community are invoked to explain the observed shift in the isotopic composition. To test the hypothesis that changes in symbiont clade could affect skeletal chemistry, additional coral samples were collected from Belize for paired Symbiodinium identification and skeletal stable isotopic analysis. We found some evidence that skeletal stable isotopic composition may be affected by symbiont clade and suggest this is an important topic for future investigation. If different Symbiodinium clades leave consistent signatures in skeletal geochemical composition, the signature will provide a method to quantify past symbiont shuffling events, important for understanding how corals are likely to respond to climate change.

  19. Geochemical and Isotopic Composition of Aerosols in Tucson

    NASA Astrophysics Data System (ADS)

    Riha, K. M.; Michalski, G. M.; Lohse, K. A.; Gallo, E. L.; Brooks, P. D.; Meixner, T.

    2010-12-01

    isotopic analyses have been conducted on these samples using the denitrifier method (Casciotti et al., 2002). Observed elevated δ18O values correspond to atmospheric oxidation processes and varying δ15N are possibly linked to different N sources. These isotopic values will be used as a proxy for deposition in a mass balance mixing model for nitrogen in arid streams. References: Casciotti, K. L., D. M. Sigman, M. G. Hastings, J. K. Böhlke and A. Hilkert, Measurement of the oxygen isotopic composition of nitrate in seawater and freshwater using the denitrifier method, Anal. Chem., 74(19), 4905-4912, 2002. Michalski, G., Z. Scott, M. Kabiling and M. Thiemens, First Measurements and Modeling of Δ17O in Atmospheric Nitrate, Geophys. Res. Lett., 30(16), (1870), 2003.

  20. Isotopic fractionation of methane in the stratosphere and its effect on free tropospheric isotopic compositions

    NASA Astrophysics Data System (ADS)

    McCarthy, M. C.; Connell, P.; Boering, K. A.

    Kinetic isotope effects (KIEs) for the oxidation of CH4 by OH, Cl, and O(¹D) were incorporated into a 2D model of the atmosphere to examine how sensitive the carbon isotopic composition of CH4 in the free troposphere is to three influences: realistic stratospheric chemistry and transport, tropospheric Cl chemistry, and use of new, experimentally-determined KIEs for the OH and O(¹D) sinks. At steady-state, our results indicate that stratospheric chemistry and transport enrich tropospheric δ13CH4 by 0.5 to 0.6‰, tropospheric Cl chemistry as modeled enriches δ13CH4 by ∼0.3‰, and the new KIE for the OH sink depletes modeled global δ13CH4 by >1‰. Ignoring the stratosphere (and Cl chemistry in general) in models therefore happens to partially compensate for use of the previously accepted KIE for OH when comparisons with observations of free tropospheric δ13CH4 are made. In contrast, including only one of these influences increases the error relative to including none. Thus, all 3 effects are of sufficient magnitude to warrant their inclusion in inverse models in order to reduce uncertainties in the CH4 budget.

  1. Influence of water-flow on skeletal isotopic compositions of branching coral Pocilopora damicornis

    NASA Astrophysics Data System (ADS)

    Suzuki, A.; Nakamura, T.; Yamasaki, H.; Minoshima, K.; Kawahata, H.

    2006-12-01

    Oxygen and carbon isotope compositions of coral skeleton appear to be more influenced by skeletal growth rate than physical conditions such as temperature in a particular setting. We examined the influence of water motion on the isotopic composition of branching coral Pocilopora damicornis grown in experimental flumes. Colony size and buoyant weight became significantly greater in the flow condition than the still condition, indicating water-flow was favorable for coral growth. Despite of the evident difference in skeletal growth rate, the skeletal oxygen isotope, carbon isotope as well, of the outer tips were almost identical between the flow- and still-treated colonies, indicating the limited influence of water-flow on the isotopic composition of active calcification site. The result suggested the potential role of light level, which was relatively high in the present experiment, for suppressing the growth-rate-related kinetic isotopic fractionation.

  2. Zinc isotopic composition of iron meteorites: Absence of isotopic anomalies and origin of the volatile element depletion

    NASA Astrophysics Data System (ADS)

    Chen, Heng; Nguyen, Bach Mai; Moynier, Frédéric

    2013-12-01

    High-precision Zn isotopic compositions measured by MC-ICP-MS are documented for 32 iron meteorites from various fractionally crystallized and silicate-bearing groups. The δ66Zn values range from -0.59‰ up to +5.61‰ with most samples being slightly enriched in the heavier isotopes compared with carbonaceous chondrites (0 < δ66Zn < 0.5). The δ66Zn versus δ68Zn plot of all samples defines a common linear fractionation line, which supports the hypothesis that Zn was derived from a single reservoir or from multiple reservoirs linked by mass-dependent fractionation processes. Our data for Redfields fall on a mass fractionation line and therefore refute a previous claim of it having an anomalous isotopic composition due to nonmixing of nucleosynthetic products. The negative correlation between δ66Zn and the Zn concentration of IAB and IIE is consistent with mass-dependent isotopic fractionation due to evaporation with preferential loss of lighter isotopes in the vapor phase. Data for the Zn concentrations and isotopic compositions of two IVA samples demonstrate that volatile depletion in the IVA parent body is not likely the result of evaporation. This is important evidence that favors the incomplete condensation origin for the volatile depletion of the IVA parent body.

  3. NEW INSIGHTS ON SATURN'S FORMATION FROM ITS NITROGEN ISOTOPIC COMPOSITION

    SciTech Connect

    Mousis, Olivier; Lunine, Jonathan I.; Fletcher, Leigh N.; Mandt, Kathleen E.; Ali-Dib, Mohamad; Atreya, Sushil

    2014-12-01

    The recent derivation of a lower limit for the {sup 14}N/{sup 15}N ratio in Saturn's ammonia, which is found to be consistent with the Jovian value, prompted us to revise models of Saturn's formation using as constraints the supersolar abundances of heavy elements measured in its atmosphere. Here we find that it is possible to account for both Saturn's chemical and isotopic compositions if one assumes the formation of its building blocks at ∼45 K in the protosolar nebula, provided that the O abundance was ∼2.6 times protosolar in its feeding zone. To do so, we used a statistical thermodynamic model to investigate the composition of the clathrate phase that formed during the cooling of the protosolar nebula and from which the building blocks of Saturn were agglomerated. We find that Saturn's O/H is at least ∼34.9 times protosolar and that the corresponding mass of heavy elements (∼43.1 M {sub ⊕}) is within the range predicted by semi-convective interior models.

  4. New Insights on Saturn's Formation from its Nitrogen Isotopic Composition

    NASA Astrophysics Data System (ADS)

    Mousis, Olivier; Lunine, Jonathan I.; Fletcher, Leigh N.; Mandt, Kathleen E.; Ali-Dib, Mohamad; Gautier, Daniel; Atreya, Sushil

    2014-12-01

    The recent derivation of a lower limit for the 14N/15N ratio in Saturn's ammonia, which is found to be consistent with the Jovian value, prompted us to revise models of Saturn's formation using as constraints the supersolar abundances of heavy elements measured in its atmosphere. Here we find that it is possible to account for both Saturn's chemical and isotopic compositions if one assumes the formation of its building blocks at ~45 K in the protosolar nebula, provided that the O abundance was ~2.6 times protosolar in its feeding zone. To do so, we used a statistical thermodynamic model to investigate the composition of the clathrate phase that formed during the cooling of the protosolar nebula and from which the building blocks of Saturn were agglomerated. We find that Saturn's O/H is at least ~34.9 times protosolar and that the corresponding mass of heavy elements (~43.1 M ⊕) is within the range predicted by semi-convective interior models.

  5. Herbivore tooth oxygen isotope compositions: Effects of diet and physiology

    NASA Astrophysics Data System (ADS)

    Kohn, Matthew J.; Schoeninger, Margaret J.; Valley, John W.

    1996-10-01

    The applicability of rapid and precise laser probe analysis of tooth enamel for δ18O has been verified, and the method has been applied to different modern herbivores in East Africa. Sampling and pretreatment procedures involve initial bleaching and grinding of enamel to <75 μm, and elimination of adsorbed water and organic compounds with BrF 5. Typical analytical reproducibilities for 0.5-2 mg samples are ±0.08‰ (± 1σ). Chemical and spectroscopic characterization of pretreated but unanalyzed samples show no alteration compared to fresh enamel. Solid reaction products are nearly pure CaF 2 with little evidence for residual O 2. Because laser probe fluorination extracts oxygen from all sites in the apatite structure (phosphate, structural carbonate, and hydroxyl), only unaltered tooth enamel (>95% apatite) can be analyzed reliably. Different East African herbivores exhibit previously unsuspected compositional differences. Average enamel δ18O values (V-SMOW) are approximately: 25‰ (goat), 27‰ (oryx), 28‰ (dikdik and zebra), 29‰ (topi), 30‰ (gerenuk), and 32‰ (gazelle). These compositions differ from generalized theoretical models, but are broadly consistent with expected isotope effects associated with differences in how much each animal (a) drinks, (b) eats C3 vs. C4 plants, and (c) pants vs. sweats. Consideration of diet, water turnover, and animal physiology will allow the most accurate interpretation of ancient teeth and targeting of environmentally-sensitive animals in paleoclimate studies.

  6. Light element isotopic compositions of cometary matter returned by the STARDUST mission

    SciTech Connect

    McKeegan, K D; Aleon, J; Bradley, J; Brownlee, D; Busemann, H; Butterworth, A; Chaussidon, M; Fallon, S; Floss, C; Gilmour, J; Gounelle, M; Graham, G; Guan, Y; Heck, P R; Hoppe, P; Hutcheon, I D; Huth, J; Ishii, H; Ito, M; Jacobsen, S B; Kearsley, A; Leshin, L A; Liu, M; Lyon, I; Marhas, K; Marty, B; Matrajt, G; Meibom, A; Messenger, S; Mostefaoui, S; Nakamura-Messenger, K; Nittler, L; Palma, R; Pepin, R O; Papanastassiou, D A; Robert, F; Schlutter, D; Snead, C J; Stadermann, F J; Stroud, R; Tsou, P; Westphal, A; Young, E D; Ziegler, K; Zimmermann, L; Zinner, E

    2006-10-10

    Hydrogen, carbon, nitrogen, and oxygen isotopic compositions are heterogeneous among comet 81P/Wild2 particle fragments, however extreme isotopic anomalies are rare, indicating that the comet is not a pristine aggregate of presolar materials. Non-terrestrial nitrogen and neon isotope ratios suggest that indigenous organic matter and highly volatile materials were successfully collected. Except for a single circumstellar stardust grain, silicate and oxide minerals have oxygen isotopic compositions consistent with solar system origin. One refractory grain is {sup 16}O-enriched like refractory inclusions in meteorites, suggesting formation in the hot inner solar nebula and large-scale radial transport prior to comet accretion in the outer solar system.

  7. Evaluation of the sulfur isotopic composition and homogeneity of the Soufre de Lacq reference material

    USGS Publications Warehouse

    Carmody, R.W.; Seal, R.R., II

    1999-01-01

    Sulfur isotopic analysis of the elemental sulfur reference material Soufre de Lacq, prepared as silver sulfide by chromous chloride reduction and as copper sulfide by sealed-tube synthesis, indicates that Soufre de Lacq is isotopically homogeneous across different size fractions to within analytical uncertainty (??0.15???). The sulfur isotopic composition of aliquots of Soufre de Lacq prepared by these two techniques are identical to within analytical uncertainty. The mean sulfur isotopic composition for Soufre de Lacq prepared as silver sulfide and copper sulfide (relative to VCDT) is +16.20 ?? 0.15??? (1??).

  8. Nutritional assessment by isotope dilution analysis of body composition

    SciTech Connect

    Szeluga, D.J.; Stuart, R.K.; Utermohlen, V.; Santos, G.W.

    1984-10-01

    The three components of body mass, body cell mass (BCM), extracellular fluid (ECF), and fat + extracellular solids (ECS: bone, tendon, etc) can be quantified using established isotope dilution techniques. With these techniques, total body water (TBW) and ECF are measured using 3H/sub 2/O and /sup 82/Bromine, respectively, as tracers. BCM is calculated from intracellular fluid (ICF) where ICF . TBW - ECF. Fat + ECS is estimated as: body weight - (BCM + ECF). TBW and ECF can be determined by either of two calculation methods, one requiring several timed plasma samples (extrapolation method) and one requiring a single plasma sample and a 4-h urine collection (urine-corrected method). The comparability of the two calculation methods was evaluated in 20 studies in 12 bone marrow transplant recipients. We found that for determination of TBW and ECF there was a very strong linear relationship (r2 greater than 0.98) between the calculation methods. Further comparisons (by t test, 2-sided) indicated that for the determination of ECF, the methods were not significantly (p greater than 0.90) different; however, TBW determined by the urine-corrected method was slightly (0.1 to 6%), but significantly (p less than 0.01) greater than that determined by the extrapolation method. Therefore, relative to the extrapolation method, the urine-corrected method ''over-estimates'' BCM and ''under-estimates'' fat + ECS since determination of these compartment sizes depends on measurement of TBW. We currently use serial isotope dilution studies to monitor the body composition changes of patients receiving therapeutic nutritional support.

  9. Reassessing the stable isotope composition assigned to methane flux from natural wetlands in isotope-constrained budgets

    NASA Astrophysics Data System (ADS)

    Hornibrook, Edward; Maxfield, Peter; Gauci, Vincent; Stott, Andrew

    2013-04-01

    Stable isotope ratios in CH4 preserve information about its origin and history, and are commonly used to constrain global CH4 budgets. Wetlands are key contributors to the atmospheric burden of CH4 and typically are assigned a stable carbon isotope composition of ~-60 permil in isotope-weighted stable isotope models despite the considerable range of δ13C(CH4) values (~ -100 to -40 permil) known to occur in these diverse ecosystems. Kinetic isotope effects (KIEs) associated with the metabolism of CH4-producing microorganisms generate much of the natural variation but highly negative and positive δ13C(CH4) values generally result from secondary processes (e.g., diffusive transport or oxidation by soil methanotrophs). Despite these complexities, consistent patterns exist in the isotope composition of wetland CH4 that can be linked conclusively to trophic status and consequently, natural succession or human perturbations that impact nutrient levels. Another challenge for accurate representation of wetlands in carbon cycle models is parameterisation of sporadic CH4 emission events. Abrupt release of large volumes of CH4-rich bubbles in short periods of time can account for a significant proportion of the annual CH4 flux from a wetland but such events are difficult to detect using conventional methods. New infrared spectroscopy techniques capable of high temporal resolution measurements of CH4 concentration and stable isotope composition can readily quantify short-lived CH4 pulses. Moreover, the isotope data can be used conclusively to determine shifts in the mode of CH4 transport and provide the potential to link initiation of abrupt emission events to forcing by internal or external factors.

  10. Investigating Tungsten Concentrations and Isotopic Compositions of Natural Water Samples from the Carson River Basin

    NASA Astrophysics Data System (ADS)

    Wasserman, N. L.; Williams, R. W.; Kayzar, T. M.; Schorzman, K. C.

    2012-12-01

    Recent studies have shown that W-isotopes may fractionate in nature1; however, the magnitude and cause of the isotopic variations are largely unknown and unconstrained. In this study, the isotopic compositions of the NIST 3163 W standard, W ore minerals, and 15 natural surface waters from Nevada's Carson River Basin were analyzed by MC-ICP-MS using external bracketing with NIST 3163 and the IUPAC 184W/183W for mass bias correction. Chemical separation procedures were developed to purify W from natural matrices and tested to assure fractionation was not introduced during column chemistry. The W isotopic compositions of these samples were measured and compared to the accepted IUPAC composition of natural W. Samples of wolframite (Fe, MnWO4) and hubnerite (MnWO4) have compositions similar to the IUPAC value but vary from the isotopic composition of NIST 3163 - particularly in 182W/183W. The isotopic compositions of the natural waters, except for an extremely evaporated sample from Soda Lake, are similar to the NIST standard. This evaporative lake, formed by a maar, has a unique chemical composition compared to other surface waters with high W (800 ± 20 ng/g) and As (1665 ± 17 ng/g) concentrations; and relatively low Fe (5.00 ± 0.13 ng/g) and Mn (0.52 ± 0.07 ng/g). These results support recent observations of natural W isotopic variation and imply that W-isotope compositions may be useful for environmental applications of stable isotope geochemistry. 1. Irisawa, K. and Hirata, T. (2006) Tungsten isotopic analysis on six geochemical reference materials using multiple collector-ICP-mass spectrometry coupled with a rhenium-external correction technique. Journal of Analytical Atomic Spectrometry 21, 1387-1395.

  11. Climatic influences on the oxygen isotopic composition of biogenic silica in prairie grass

    NASA Astrophysics Data System (ADS)

    Webb, Elizabeth A.; Longstaffe, Fred J.

    2002-06-01

    Samples of Calamovilfa longifolia were collected from across the North American prairies to investigate the relationship between the oxygen-isotope composition of biogenic silica (phytoliths) deposited in this grass and relative humidity, temperature, and the oxygen-18 enrichment of soil water relative to local precipitation. The δ 18O values of silica in nontranspiring tissues were controlled by soil-water composition and temperature, whereas the oxygen-18 content of silica formed in leaf and inflorescence tissues was enriched further by transpiration. Accurate calculation of growing temperature was possible only when the oxygen-isotope compositions of both stem silica and soil water were known. However, the oxygen-isotope values of stem phytoliths can be used to calculate the variation in the isotopic composition of soil water across a North American temperature gradient. As plant organic matter decays and phytoliths are transferred to the soil, the temperature and soil-water signals carried by the oxygen-isotope composition of silica from nontranspiring tissues can be masked by the oxygen-18 enrichment of phytoliths from transpiring tissues. However, the overall oxygen-isotope composition of a soil-phytolith assemblage can be related to temperature using an empirical relationship based on temperature and the difference between soil-phytolith and estimated soil-water oxygen-isotope compositions.

  12. Heterogeneous magnesium isotopic composition of the lower continental crust: A xenolith perspective

    NASA Astrophysics Data System (ADS)

    Teng, Fang-Zhen; Yang, Wei; Rudnick, Roberta L.; Hu, Yan

    2013-09-01

    We report 26 high-precision whole-rock Mg isotopic analyses for two suites of well-characterized granulite xenoliths from Chudleigh and McBride, North Queensland, Australia, in order to constrain the behavior of Mg isotopes during deep crustal processes and the Mg isotopic composition of the lower continental crust. Previous studies suggest that the Chudleigh granulites are a suite of cogenetic cumulates crystallized from mafic magmas that intruded into and assimilated the preexisting lower crust via combined assimilation and fractional crystallization (AFC). The δ26Mg values of the xenoliths range from -0.31 to -0.21‰ and correlate with radiogenic isotopes, reflecting mixing of mantle-derived mafic magma (δ26Mg = -0.31‰) with preexisting isotopically heavy crustal materials (δ26Mg = ˜ +0.5‰) through the AFC process. The McBride granulites range compositionally from mafic to felsic, and originated as cumulates, solidified mafic/felsic melts, and restites that formed during basaltic underplating and reworking of preexisting lower crust. Their δ26Mg values vary widely from -0.72 to +0.19‰. The large Mg isotopic variation in the McBride xenoliths reflects both distinct source compositions and metamorphic enrichment of garnet, which is isotopically light. Based on these results, the lower continental crust has a heterogeneous Mg isotopic composition, with a weighted average δ26Mg of -0.18‰. The bulk continental crust, based on available data, has an average Mg isotopic composition of -0.19‰, and is slightly heavier than the mantle. The highly heterogeneous Mg isotopic distribution in the crust indicates that chemical weathering not only modifies the upper crust compositions but also significantly influences lower crust compositions through emplacement of upper crustal materials into the deep crust.

  13. Herbivore tooth oxygen isotope compositions: Effects of diet and physiology

    SciTech Connect

    Kohn, M.J.; Valley, J.W.; Schoeninger, M.J.

    1996-10-01

    The applicability of rapid and precise laser probe analysis of tooth enamel for {delta}{sup 18}O has been verified, and the method has been applied to different modern herbivores in East Africa. Sampling and pretreatment procedures involve initial bleaching and grinding of enamel to <75 {mu}m, and elimination of adsorbed water and organic compounds with BrF{sub 5}. Typical analytical reproducibilities for 0.5-2 mg samples are {+-}0.08{per_thousand} ({+-} 1{sigma}). Chemical and spectroscopic characterization of pretreated but unanalyzed samples show no alteration compared to fresh enamel. Solid reaction products are nearly pure CaF{sub 2} with little evidence for residual O{sub 2}. Because laser probe fluorination extracts oxygen from all sites in the apatite structure (phosphate, structural carbonate, and hydroxyl), only unaltered tooth enamel ( >95% apatite) can be analyzed reliably. Different East African herbivores exhibit previously unsuspected compositional differences. Average enamel {delta}{sup 18}O values (V-SMOW) are approximately: 25{per_thousand} (goat). 27{per_thousand} (oryx), 28{per_thousand} (dikdik and zebra), 29{per_thousand} (topi), 30{per_thousand} (gerenuk), and 32{per_thousand} (gazelle). These compositions differ from generalized theoretical models, but are broadly consistent with expected isotope effects associated with differences in how much each animal (a) drinks, (b) eats C3 vs. C4 plants, and (c) pants vs. sweats. Consideration of diet, water turnover. and animal physiology will allow the most accurate interpretation of ancient teeth and targeting of environmentally-sensitive animals in paleoclimate studies. 66 refs., 2 figs., 2 tabs.

  14. Factors affecting the hydrogen isotopic composition of dissolved organic matter along a salinity gradient

    NASA Astrophysics Data System (ADS)

    Debond, A. A.; Ziegler, S. E.; Fogel, M. L.; Morrill, P. L.; Bowden, R.

    2010-12-01

    The role of terrestrial dissolved organic matter (DOM) in regulating estuarine ecosystem processes is poorly understood, in part due to difficulties in tracking terrestrial DOM in marine environments. Analysis of multiple stable isotopes (C, N, S) is often required due to poor separation of the carbon isotope signatures of marine and terrestrial sources. However, hydrogen isotopes exhibit greater fractionation. Marine DOM sources have a hydrogen isotope signature of 0‰ while terrestrial DOM can have signatures of up to -270‰ at the poles. Some challenges must be addressed before hydrogen isotopes can be used to track terrestrial DOM in aquatic environments. Hydrogen isotopes may undergo exchange between water and organic matter, obscuring terrestrial signatures. Riverine discharge into marine environments introduces terrestrial DOM to water of different chemical and isotopic compositions which could influence the isotopic composition of the terrestrial DOM. We investigate the effects of changes in water isotopic composition on DOM by introducing terrestrial DOM to freshwaters of isotopic compositions up to +1000‰ for up to two months. We also use surface water samples along a salinity transect at the Salmonier Arm, Newfoundland, Canada to investigate the effects of changes in water mass conditions (pH, salinity and water isotopes) on terrestrial DOM. In addition to changes in water mass conditions, methods for isolating estuarine DOM may regulate affect its isotopic composition. Ultrafiltration (UF), a size-exclusion technique, has been shown to isolate and concentrate the largest proportion of DOM in estuarine environments. UF separates DOM into low molecular weight (LMW, <1kDa) and high molecular weight (HMW, >1kDa) fractions. However, under certain processing conditions, some LMW DOM can be retained. During desalting (diafiltration), LMW DOM continues to be removed from the concentrate, whereas HMW DOM is retained. The proportion of LMW DOM retained

  15. Investigating the Source, Transport, and Isotope Composition of Water in the Atmospheric Boundary Layer

    NASA Astrophysics Data System (ADS)

    Griffis, T. J.; Schultz, N. M.; Lee, X.

    2011-12-01

    The isotope composition of water (liquid and vapor phases) can provide important insights regarding the source of water used by plants, the origins of atmospheric water vapor, and the sources of carbon dioxide. In recent years there have been significant advances in the ability to quantify the isotope composition of water and water vapor using optical isotope techniques. We have used and helped develop some of these techniques to determine the isotope composition of soil and plant waters, to measure the isoflux of water vapor between the land surface and atmosphere, and to examine the isotope composition of water vapor and deuterium excess in the atmospheric boundary layer. In this presentation we will discuss three related issues: 1) Identification and correction of spectral contamination in soil and plant water samples using optical techniques; 2) The benefits and practical limitations of quantifying the isotope composition of evapotranspiration using the eddy covariance approach; and 3) The scientific value and feasibility of tracking the long-term (seasonal and interannual) behavior of the isotope composition of water vapor and deuterium excess in the atmospheric boundary layer. A few short stories will be provided from experiments conducted in the lab, at the field scale, and from a very tall tower at the University of Minnesota from 2008 to 2011.

  16. Oxygen isotopic composition and U-Pb discordance in zircon

    USGS Publications Warehouse

    Booth, A.L.; Kolodny, Y.; Chamberlain, C.P.; McWilliams, M.; Schmitt, A.K.; Wooden, J.

    2005-01-01

    We have investigated U-Pb discordance and oxygen isotopic composition of zircon using high-spatial resolution ??18O measurement by ion microprobe. ??18O in both concordant and discordant zircon grains provides an indication of the relationship between fluid interaction and discordance. Our results suggest that three characteristics of zircon are interrelated: (1) U-Pb systematics and concomitant age discordance, (2) ??18O and the water-rock interactions implied therein, and (3) zircon texture, as revealed by cathodoluminescence and BSE imaging. A key observation is that U-Pb-disturbed zircons are often also variably depleted in 18O, but the relationship between discordance and ??18O is not systematic. ??18O values of discordant zircons are generally lighter but irregular in their distribution. Textural differences between zircon grains can be correlated with both U-Pb discordance and ??18O. Discordant grains exhibit either a recrystallized, fractured, or strongly zoned CL texture, and are characteristic of 18O depletion. We interpret this to be a result of metamictization, leading to destruction of the zircon lattice and an increased susceptibility to lead loss. Conversely, grains that are concordant have less-expressed zoning and a smoother CL texture and are enriched in 18O. From this it is apparent that various stages of water-rock interaction, as evidenced by systematic variations in ??18O, leave their imprint on both the texture and U-Pb systematics of zircon. Copyright ?? 2005 Elsevier Ltd.

  17. Hydrogen and oxygen in brine shrimp chitin reflect environmental water and dietary isotopic composition

    NASA Astrophysics Data System (ADS)

    Nielson, Kristine E.; Bowen, Gabriel J.

    2010-03-01

    Hydrogen and oxygen isotope ratios of the common structural biopolymer chitin are a potential recorder of ecological and environmental information, but our understanding of the mechanisms of incorporation of H and O from environmental substrates into chitin is limited. We report the results of a set of experiments in which the isotopic compositions of environmental water and diet were varied independently in order to assess the contribution of these variables to the H and O isotopic composition of Artemia franciscana chitin. Hydrogen isotope ratios of chitin were strongly linearly correlated with both food and water, with approximately 26% of the hydrogen signal reflecting food and approximately 38% reflecting water. Oxygen isotopes were also strongly correlated with the isotopic composition of water and food, but whereas 69% of oxygen in chitin exchanged with environmental water, only 10% was derived from food. We propose that these observations reflect the position-specific, partial exchange of H and O atoms with brine shrimp body water during the processes of digestion and chitin biosynthesis. Comparison of culture experiments with a set of natural samples collected from the Great Salt Lake, UT in 2006 shows that, with some exceptions, oxygen isotope compositions of chitin track those of water, whereas hydrogen isotopes vary inversely with those of lake water. The different behavior of the two isotopic systems can be explained in terms of a dietary shift from allochthonous particulate matter with relatively higher δ 2H values in the early spring to autochthonous particulate matter with significantly lower δ 2H values in the late summer to autumn. These results suggest oxygen in chitin may be a valuable proxy for the oxygen isotopic composition of environmental water, whereas hydrogen isotope values from the same molecule may reveal ecological and biogeochemical changes within lakes.

  18. The iron isotope composition of enstatite meteorites: Implications for their origin and the metal/sulfide Fe isotopic fractionation factor

    NASA Astrophysics Data System (ADS)

    Wang, Kun; Savage, Paul S.; Moynier, Frédéric

    2014-10-01

    Despite their unusual chemical composition, it is often proposed that the enstatite chondrites represent a significant component of Earth’s building materials, based on their terrestrial similarity for numerous isotope systems. In order to investigate a possible genetic relationship between the Fe isotope composition of enstatite chondrites and the Earth, we have analyzed 22 samples from different subgroups of the enstatite meteorites, including EH and EL chondrites, aubrites (main group and Shallowater) and the Happy Canyon impact melt. We have also analyzed the Fe isotopic compositions of separated (magnetic and non-magnetic) phases from both enstatite chondrites and achondrites. On average, EH3-5 chondrites (δ56Fe = 0.003 ± 0.042‰; 2 standard deviation; n = 9; including previous literature data) as well as EL3 chondrites (δ56Fe = 0.030 ± 0.038‰; 2 SD; n = 2) have identical and homogeneous Fe isotopic compositions, indistinguishable from those of the carbonaceous chondrites and average terrestrial peridotite. In contrast, EL6 chondrites display a larger range of isotopic compositions (-0.180‰ < δ56Fe < 0.181‰; n = 11), a result of mixing between isotopically distinct mineral phases (metal, sulfide and silicate). The large Fe isotopic heterogeneity of EL6 is best explained by chemical/mineralogical fragmentation and brecciation during the complex impact history of the EL parent body. Enstatite achondrites (aubrites) also exhibit a relatively large range of Fe isotope compositions: all main group aubrites are enriched in the light Fe isotopes (δ56Fe = -0.170 ± 0.189‰; 2 SD; n = 6), while Shallowater is, isotopically, relatively heavy (δ56Fe = 0.045 ± 0.101‰; 2 SD; n = 4; number of chips). We take this variation to suggest that the main group aubrite parent body formed a discreet heavy Fe isotope-enriched core, whilst the Shallowater meteorite is most likely from a different parent body where core and silicate material remixed. This could be

  19. Soil drying effects on the carbon isotope composition of soil respiration

    EPA Science Inventory

    Stable isotopes are used widely as a tool for determining sources of carbon (C) fluxes in ecosystem C studies. Environmental factors that change over time, such as moisture, can create dynamic changes in the isotopic composition of C assimilated by plants, and offers a unique opp...

  20. Non-chondritic sulphur isotope composition of the terrestrial mantle.

    PubMed

    Labidi, J; Cartigny, P; Moreira, M

    2013-09-12

    Core-mantle differentiation is the largest event experienced by a growing planet during its early history. Terrestrial core segregation imprinted the residual mantle composition by scavenging siderophile (iron-loving) elements such as tungsten, cobalt and sulphur. Cosmochemical constraints suggest that about 97% of Earth's sulphur should at present reside in the core, which implies that the residual silicate mantle should exhibit fractionated (34)S/(32)S ratios according to the relevant metal-silicate partition coefficients, together with fractionated siderophile element abundances. However, Earth's mantle has long been thought to be both homogeneous and chondritic for (34)S/(32)S, similar to Canyon Diablo troilite, as it is for most siderophile elements. This belief was consistent with a mantle sulphur budget dominated by late-accreted chondritic components. Here we show that the mantle, as sampled by mid-ocean ridge basalts from the south Atlantic ridge, displays heterogeneous (34)S/(32)S ratios, directly correlated to the strontium and neodymium isotope ratios (87)Sr/(86)Sr and (143)Nd/(144)Nd. These isotope trends are compatible with binary mixing between a low-(34)S/(32)S ambient mantle and a high-(34)S/(32)S recycled component that we infer to be subducted sediments. The depleted end-member is characterized by a significantly negative δ(34)S of -1.28 ± 0.33‰ that cannot reach a chondritic value even when surface sulphur (from continents, altered oceanic crust, sediments and oceans) is added. Such a non-chondritic (34)S/(32)S ratio for the silicate Earth could be accounted for by a core-mantle differentiation record in which the core has a (34)S/(32)S ratio slightly higher than that of chondrites (δ(34)S = +0.07‰). Despite evidence for late-veneer addition of siderophile elements (and therefore sulphur) after core formation, our results imply that the mantle sulphur budget retains fingerprints of core-mantle differentiation. PMID:24005324

  1. Isotope composition (C, H, O) and gas potential assessment in the South Caspian depression (Azerbaijan)

    NASA Astrophysics Data System (ADS)

    Poletayev, A. V.

    2009-04-01

    The large amount of HC isotope composition material of over 330 samples allows to study gas potential assessment within the South Caspian depression. Maps of isotope composition changes according to area extent, as well as graphs of HC distribution depending upon stratigraphic age including rocks, graphs of isotope composition change on sampling depth were compiled for HC study and oil-gas deposits formation. Comparison of mud volcanoes gases, oil and gas fields, gas-hydrates and bottom sediments was conducted. Gases genesis according to M. Shoelle and A. James methodic was studied. Model of area paleoconstruction was studied. Comparison of mud volcanoes gases with gases of oil fields within South Caspian depression shows that their isotope composition varies within the same ranges. Their difference is observed in chemical composition. Mud volcanoes gases are sharply impoverished by amount of heavy hydrocarbons. Study of isotope gases composition distribution in extent area allowed to distinguish zones and areas with different composition of heavy isotope. For example, in the deep-seated areas of the South Caspian depression toward flank zones of Low Kura depression as well some areas of Baku archipelago and Absheron peninsula gradually one can observe zones with a low content of heavy carbon isotope etc. Isotope gases composition depending upon stratigraphic age of including rocks has a certain peculiarities. From low to the upper section of PS as well as deposits of Cretaceous system toward chokrak regiostage (underlying PS deposits) one can observe increase of light carbon isotope. This fact allows to suppose that there exits two stages of HC formation. Comparison of HC gases isotope composition with sampling depth allowed to conclude that in the near-flank zones oil-gas deposits were re-formed by a large gas volumes the source of which was there same deposits within new thermobaric conditions. Gases of biochemical, diagenetic and thermocatalytic genesis etc

  2. Triple-Point Temperature and the Isotopic Composition of Three Commercial Neon Gases

    NASA Astrophysics Data System (ADS)

    Yang, I.; Gam, K. S.; Joung, W.; Kim, Y.-G.

    2015-08-01

    The triple-point temperature of neon, , is known to have dependence on the isotopic composition. Recently, the Technical Annex for the International Temperature Scale of 1990 was updated to specify the method of correction for the isotopic reference ratio of neon. In this study, to confirm this correction in the Technical Annex independently, the effects of the isotopic composition of neon on for three commercial neon gas sources were studied. For the measurement of the isotopic composition, a gas mass spectrometer was used to compare the sample gases with a reference neon gas whose isotopic composition was known with high precision by a gravimetric method. For the measurement of , an open-cell type cryostat for the realization of low-temperature fixed points was used. The physical cell and the thermal environment around it remained very similar for all measurements with the neon gases due to the nature of the open-cell type system. Therefore, the difference in among different samples could be measured with a relatively low uncertainty, canceling many systematic effects that are common to all measurements. Our result was consistent with the correction in the Technical Annex. Furthermore, because one of the commercial neon gases was the bottle that was used for KRISS measurements in the international comparison CCT-K2, it is now possible to correct the measurement for the reference isotopic ratio and compare it with other measurements for which isotopic composition data are available.

  3. The Pb isotopic compositions of lower crustal xenoliths and the evolution of lower crustal Pb

    NASA Astrophysics Data System (ADS)

    Rudnick, Roberta L.; Goldstein, Steven L.

    1990-05-01

    Pb isotopic compositions for three suites of well-characterized granulite facies xenoliths from a diversity of crustal settings (the Chudleigh and McBride volcanic provinces, Queensland, Australia and the Eifel volcanics, West Germany) are presented here. All three suites plot to the right of the 4.57 Ga geochron, similar to the published Pb results of other mafic granulite xenoliths. Correlations between Sr, Nd and Pb isotopes in the three suites measured here point to an origin by mixing of mantle-derived basaltic magmas with lower crust at the time of basaltic underplating (i.e., < 100 Ma for Chudleigh, ˜ 300 Ma for McBride, ˜ 450 Ma for Eifel). Because the Pb concentration of the continental crust is much greater than that of mantle-derived basaltic magmas, the Pb isotopic compositions of the magmas are shifted dramatically by the mixing, allowing delineation of the isotopic characteristics of the lower crust. In all three cases, this lower crust had radiogenic Pb and Sr isotopic compositions and unradiogenic Nd isotopic compositions, yielding Proterozoic Nd model ages. Such radiogenic lower crust contrasts markedly with the Pb isotopic characteristics of most Precambrian granulite facies terrains. Whereas the Nd isotopes reflect the average age of crust formation, the Pb isotopic characteristics of the lower crust appear to be a function of the tectonothermal age of the crust: unradiogenic Pb can only develop in regions which have remained stable for long time periods (e.g., cratons), whereas in areas where orogenies have occurred subsequent to crustal formation, the Pb isotopic composition of the lower crust is "rejuvenated" through mixing with radiogenic Pb from upper crust and mantle-derived magmas. Thus, after orogeny, the Pb isotopic composition of the lower crust resembles that of the upper crust. On the basis of this proposed orogenic age-Pb isotope correlation, we estimate the Pb isotopic composition of the lower crust using the data for granulite

  4. Monitoring the water vapor isotopic composition in the temperate North Atlantic

    NASA Astrophysics Data System (ADS)

    Sveinbjörnsdottir, Arny E.; Steen-Larsen, Hans Christian; Jonsson, Thorsteinn; Johnsen, Sigfus J.

    2013-04-01

    Water stable isotopes have during many decades been used as climate proxies and indicators for variations in the hydrological cycle. However we are to a great extent still using simple empirical relationships without any deeper theoretical understanding. In order to properly relate changes in the climate and hydrological cycle to changes in the observed stable water isotopic signal we must understand the underlying physical processes. Furthermore it is a challenge for General Climate Models to adequately represent the isotopes in the hydrological cycle because of lack of in-situ measurements of the atmospheric water-vapor composition in the source regions. During the fall of 2010 we installed an autonomous water vapor spectroscopy laser (from Los Gatos Research) in a lighthouse on the South Coast of Iceland (63.83 N 21.47W) with the plan to be operational for several years. The purpose of this installation was through monitoring of the water vapor isotopic composition to understand the physical processes governing the isotopic composition of the water vapor evaporated from the ocean as well as the processes of mixing between the free troposphere and marine boundary layer. Because of the remoteness of the monitoring site and simple topography we are able to isolate the 'fingerprint' on the isotopic signal in the water vapor from respectively the ocean and the interior highland leading to a near perfect case-study area. Using back-trajectories we find a strong influence of the origin of the air masses on the measured isotopic composition. The mixing of the marine-boundary layer is found to strongly influence the measured isotopic composition. The second order isotopic parameter, d-excess, is contrary to theory and previous observations found not to depend on the relative humidity. However we do find a good correlation between the d-excess and the measured isotopic composition. We speculate that the lack of correlation between d-excess and relative humidity can be

  5. Monitoring the water vapor isotopic composition in the temperate North Atlantic

    NASA Astrophysics Data System (ADS)

    Steen-Larsen, H. C.; Sveinbjörnsdottir, A. E.; Jónsson, T. H.; Johnsen, S. J.

    2012-04-01

    Water stable isotopes have during many decades been used as climate proxies and indicators for variations in the hydrological cycle. However we are to a great extent still using simple empirical relationships without any deeper theoretical understanding. In order to properly relate changes in the climate and hydrological cycle to changes in the observed stable water isotopic signal we must understand the underlying physical processes. Furthermore it is a challenge for General Climate Models to adequately represent the isotopes in the hydrological cycle because of lack of in-situ measurements of the atmospheric water-vapor composition in the source regions. During the fall of 2010 we installed an autonomous water vapor spectroscopy laser (from Los Gatos Research) in a lighthouse on the South Coast of Iceland (63.83 N 21.47W) with the plan to be operational for several years. The purpose of this installation was through monitoring of the water vapor isotopic composition to understand the physical processes governing the isotopic composition of the water vapor evaporated from the ocean as well as the processes of mixing between the free troposphere and marine boundary layer. Because of the remoteness of the monitoring site and simple topography we are able to isolate the 'fingerprint' on the isotopic signal in the water vapor from respectively the ocean and the interior highland leading to a near perfect case-study area. Using back-trajectories we find a strong influence of the origin of the air masses on the measured isotopic composition. The mixing of the marine-boundary layer is found to strongly influence the measured isotopic composition. The second order isotopic parameter, d-excess, is contrary to theory and previous observations found not to depend on the relative humidity. However we do find a good correlation between the d-excess and the measured isotopic composition. We speculate that the lack of correlation between d-excess and relative humidity can be

  6. Non-destructive measurement of carbonic anhydrase activity and the oxygen isotope composition of soil water

    NASA Astrophysics Data System (ADS)

    Jones, Sam; Sauze, Joana; Ogée, Jérôme; Wohl, Steven; Bosc, Alexandre; Wingate, Lisa

    2016-04-01

    Carbonic anhydrases are a group of metalloenzymes that catalyse the hydration of aqueous carbon dioxide (CO2). The expression of carbonic anhydrase by bacteria, archaea and eukarya has been linked to a variety of important biological processes including pH regulation, substrate supply and biomineralisation. As oxygen isotopes are exchanged between CO2 and water during hydration, the presence of carbonic anhydrase in plants and soil organisms also influences the oxygen isotope budget of atmospheric CO2. Leaf and soil water pools have distinct oxygen isotope compositions, owing to differences in pool sizes and evaporation rates, which are imparted on CO2during hydration. These differences in the isotopic signature of CO2 interacting with leaves and soil can be used to partition the contribution of photosynthesis and soil respiration to net terrestrial CO2 exchange. However, this relies on our knowledge of soil carbonic anhydrase activity and currently, the prevalence and function of these enzymes in soils is poorly understood. Isotopic approaches used to estimate soil carbonic anhydrase activity typically involve the inversion of models describing the oxygen isotope composition of CO2 fluxes to solve for the apparent, potentially catalysed, rate of oxygen exchange during hydration. This requires information about the composition of CO2 in isotopic equilibrium with soil water obtained from destructive, depth-resolved soil water sampling. This can represent a significant challenge in data collection given the considerable potential for spatial and temporal variability in the isotopic composition of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by constraining carbonic anhydrase activity and the composition of soil water in isotopic equilibrium with CO2 by solving simultaneously the mass balance for two soil CO2 steady states differing only in the

  7. Isotopic Composition of Presolar Silicon Carbide Grains Analyzed with CHILI

    NASA Astrophysics Data System (ADS)

    Stephan, T.; Trappitsch, R.; Davis, A. M.; Pellin, M. J.; Rost, D.; Savina, M. R.; Jadhav, M.; Kelly, C. H.

    2015-07-01

    Twenty-two presolar SiC grains were analyzed for Sr, Zr, and Ba isotopes with the Chicago Instrument for Laser Ionization. Most grains showed isotope patterns consistent with formation in AGB star like observed previously. One grain is a supernova grain.

  8. Isotopic composition of Pb and Th in interplinian volcanics from Somma-Vesuvius volcano, Italy

    USGS Publications Warehouse

    Cortini, M.; Ayuso, R.A.; de Vivo, B.; Holden, P.; Somma, R.

    2004-01-01

    We present a detailed isotopic study of volcanic rocks emitted from Somma-Vesuvius volcano during three periods of interplinian activity: "Protohistoric" (3550 y B.P. to 79 A.D.), "Ancient Historic" (79 to 472 A.D.) and "Medieval" (472 to 1631 A.D.). Pb isotopic compositions of two acid leached fractions and whole rock residues of 37 whole rock samples (determined by Somma et al., 2001) show that each of the three interplinian periods is distinguished by small, systematic, and unique uranogenic and thorogenic Pb isotopic trends. This key and novel feature is compatible with the notion that the Pb isotopic data reflect small-scale source heterogeneity operating over relatively short periods of time. From this representative group of samples, a selected set of nine whole rocks were analysed for Th isotopes. 232Th/238U ratios in the source can be obtained independently from Pb and from Th isotopes. Those obtained from Pb isotopes represent source ratios, time-integrated over the whole age of the Earth; they range from 3.9 to 4.1. 232Th/238U obtained from Th isotopes are those of the present source. They are lower, and cluster around 3.5; this difference probably indicates recent U enrichment of the present source. The behaviour of Pb, as inferred by its isotopic ratios, is quite distinct from that of Sr and Nd isotopes: Pb isotope variations are not correlated to Sr or Nd isotope variations. The isotopic contrast is compatible with the idea that the isotopes were decoupled during magmatic production, evolution, and ascent through the crust. Thus, the Pb isotopes do not reflect the effects of the same processes as in the case of the Sr and Nd isotopes, or, as we also favor, they do not necessarily reflect the same source contributions into the magmas. Moreover, the Pb isotopic evolution of the interplinian rocks chiefly reflects mixing, driven by processes that are superimposed on, and independent of, other source contributions that determine the isotopic compositions

  9. The effect of small scale variablity in isotopic composition of precipitation on hydrograph separation results

    NASA Astrophysics Data System (ADS)

    Fischer, Benjamin; van Meerveld, Ilja; Seibert, Jan

    2016-04-01

    Understanding runoff processes is important for predictions of streamflow quantity and quality. The two-component isotope hydrograph separation (IHS) method is a valuable tool to study how catchments transform rainfall into runoff. IHS allows the stormflow hydrograph to be separated into rainfall (event water) and water that was stored in the catchment before the event (pre-event water). To be able to perform an IHS, water samples of baseflow (pre-event water) and stormflow are collected at the stream outlet. Rainfall is usually collected at one location by hand as an event total or sampled sequentially during the event. It is usually assumed that the spatial variability in rainfall and the isotopic composition of rainfall are negligible for small (<10km2) catchments. However, different studies have shown that precipitation can vary within short distances. Subsequently it remains unclear how the spatio-temproal variability of rainfall and the stable isotope composition of rainfall affect the results of an IHS. In this study, we investigated the effects of the spatio-temporal variability in the isotopic composition of rainfall across a small headwater catchment in Switzerland. Rainfall was measured at eight locations and three streams (catchment area of 0.15, 0.23, and 0.7 km2). The isotopic composition of rainfall and streamflow were sampled for 10 different rain events (P: 5 mm intervals, Q: 12 to 51 samples per events). This dataset was used to perform a two-component isotope hydrograph separation. The results show that for some events the spatial variability in total rainfall, mean and maximum rainfall intensity and stable isotope composition of rainfall was high. There was no relation between the stable isotope composition of rainfall and the rainfall sum, rainfall intensity or altitude. The spatial variability of the isotopic composition of rainfall was for 4 out of the 10 events as large as the temporal variability in the isotopic composition. Different

  10. The stable isotope composition of transpired water and the rate of change in leaf water enrichment in response to variable environments

    NASA Astrophysics Data System (ADS)

    Simonin, K. A.; Roddy, A. B.; Link, P.; Apodaca, R. L.; Tu, K. P.; Hu, J.; Dawson, T. E.; Barbour, M.

    2012-12-01

    Previous research has shown that during daylight hours the isotope composition of leaf water is generally well approximated by steady-state leaf water isotope enrichment models. However, there is little direct confirmation of isotopic steady state (ISS) transpiration. Here we use a novel method to evaluate the frequency (or infrequency) of ISS transpiration and the rate of change in leaf water enrichment when leaves are exposed to a variable environment. Specifically, our study had three goals. First, we wanted to develop a new method to measure the isotope fluxes of transpiration that relies on isotope ratio infrared spectroscopy (IRIS) and highlight how an IRIS instrument can be coupled to plant gas exchange systems. In doing so, we also developed a method for controlling the absolute humidity entering the gas exchange cuvettes across a wide range of concentrations (approximately 4000 ppmv to 22000 ppmv) without changing the isotope composition of water vapour entering the cuvette. Second, we quantified variation in the isotope composition of transpired water vapor and the rate of change in leaf water enrichment that can occur as a result of changes in relative humidity, leaf surface conductance to water vapour, leaf temperature and the isotope composition of atmospheric water vapor. Third, we examine the differences between steady state and non-steady state model predictions of leaf water enrichment at the site of evaporation. In our measurements the isotopic compositions of transpired water were neither stable nor equal to source water until leaves had been maintained at physiological steady state for at least 40 minutes. Additionally when transpiration was not at ISS, the steady state model predictions of leaf water enrichment at the site of evaporation exceeded non steady-state model predictions by up to 8 per mil. Further, the rate of change in leaf water enrichment was highly sensitive to variation in leaf water content. Our results suggest that a variable

  11. Changes in Oxygen Isotopes Composition of Precipitation over Tibetan Plateau during Cenozoic

    NASA Astrophysics Data System (ADS)

    Botsyun, S.; Sepulchre, P.; Donnadieu, Y.; Risi, C. M.; Fluteau, F.

    2014-12-01

    Despite the increasing role of the stable oxygen isotopes measurements for reconstructing mountains belts paleoelevation, some issues remain that lead to a large uncertainty in paleoelevation estimationes. Among them, the use of modern isotopic lapse rate with no account of climate change linked to lower topography can lead to misinterpretation of uplift rates. In this study, we use the atmospheric general circulation model LMDZ-iso to simulate changes in isotopic composition of precipitation due to uplift of the Himalayas and Tibetan plateau. Various scenarios of TP growth have been applied together with Paleocene, Eocene, Oligocene and Miocene boundary conditions. Our simulations allow us to estimate the magnitude of precipitation, temperature and wind field changes related to the spatial and temporal evolution of the Tibetan Plateau and Himalayas. Such changes affected the isotopic composition of precipitation during the Cenozoic.We investigate the impact of these changes on the isotopic lapse rate and the implications for paleoelevation estimates.

  12. Absolute quantification of Pru av 2 in sweet cherry fruit by liquid chromatography/tandem mass spectrometry with the use of a stable isotope-labelled peptide.

    PubMed

    Ippoushi, Katsunari; Sasanuma, Motoe; Oike, Hideaki; Kobori, Masuko; Maeda-Yamamoto, Mari

    2016-08-01

    Pru av 2, a pathogenesis-related (PR) protein present in the sweet cherry (Prunus avium L.) fruit, is the principal allergen of cherry and one of the chief causes of pollen food syndrome (oral allergy syndrome). In this study, a quantitative assay for this protein was developed with the use of the protein absolute quantification (AQUA) method, which consists of liquid chromatography/tandem mass spectrometry (LC/MS/MS) employing TGC[CAM]STDASGK[(13)C6,(15)N2], a stable isotope-labelled internal standard (SIIS) peptide. This assay gave a linear relationship (r(2)>0.99) in a concentration range (2.3-600fmol/μL), and the overall coefficient of variation (CV) for multiple tests was 14.6%. Thus, the contents of this allergenic protein in sweet cherry products could be determined using this assay. This assay should be valuable for allergological investigations of Pru av 2 in sweet cherry and detection of protein contamination in foods. PMID:26988485

  13. Bio-generation of stable isotope-labeled internal standards for absolute and relative quantitation of phase II drug metabolites in plasma samples using LC-MS/MS.

    PubMed

    Li, Pei; Li, Zi; Beck, Wayne D; Callahan, Patrick M; Terry, Alvin V; Bar-Peled, Maor; Bartlett, Michael G

    2015-05-01

    Quantification of drug metabolites in biological samples has been of great interest in current pharmaceutical research, since metabolite concentrations and pharmacokinetics can contribute to a better understanding of the toxicity of drug candidates. Two major categories of Phase II metabolites, glucuronide conjugates and glutathione conjugates, may cause significant drug toxicity and therefore require close monitoring at early stages of drug development. In order to achieve high precision, accuracy, and robustness, stable isotope-labeled (SIL) internal standards (IS) are widely used in quantitative bioanalytical methods using liquid chromatography and tandem mass spectrometry (LC-MS/MS), due to their capability of compensating for matrix effects, extraction variations and instrument response fluctuations. However, chemical synthesis of SIL analogues of Phase II metabolites can often be very difficult and require extensive exploratory research, leading to higher cost and significant delays in drug research and development. To overcome these challenges, we have developed a generic method which can synthesize SIL analogues of Phase II metabolites from more available SIL parent drugs or SIL conjugation co-factors, using in vitro biotransformation. This methodology was successfully applied to the bio-generation of SIL glucuronide conjugates and glutathione conjugates. The method demonstrated satisfactory performance in both absolute quantitation and assessment of relative exposure coverage across species in safety tests of drug metabolites (MIST). This generic technique can be utilized as an alternative to chemical synthesis and potentially save time and cost for drug research and development. PMID:25804729

  14. Calcium and Oxygen Isotopic Composition of Calcium Carbonates

    NASA Astrophysics Data System (ADS)

    Niedermayr, Andrea; Eisenhauer, Anton; Böhm, Florian; Kisakürek, Basak; Balzer, Isabelle; Immenhauser, Adrian; Jürgen Köhler, Stephan; Dietzel, Martin

    2016-04-01

    Different isotopic systems are influenced in multiple ways corresponding to the crystal structure, dehydration, deprotonation, adsorption, desorption, isotope exchange and diffusion processes. In this study we investigated the structural and kinetic effects on fractionation of stable Ca- and O-isotopes during CaCO3 precipitation. Calcite, aragonite and vaterite were precipitated using the CO2 diffusion technique[1]at a constant pH of 8.3, but various temperatures (6, 10, 25 and 40° C) and precipitation rates R (101.5 to 105 μmol h‑1 m‑2). The calcium isotopic fractionation between solution and vaterite is lower (Δ44/40Ca= -0.10 to -0.55 ‰) compared to calcite (-0.69 to -2.04 ‰) and aragonite (-0.91 to -1.55 ‰). In contrast the fractionation of oxygen isotopes is highest for vaterite (32.1 ‰), followed by aragonite (29.2 ‰) and calcite (27.6 ‰) at 25° C and equilibrium. The enrichment of 18O vs. 16O in all polymorphs decreases with increasing precipitation rate by around -0.7 ‰ per log(R). The calcium isotopic fractionation between calcite/ vaterite and aqueous Ca2+ increases with increasing precipitation rate by ˜0.45 ‰ per log(R) and ˜0.1 ‰ per log(R) at 25° C and 40° C, respectively. In contrast the fractionation of Ca-isotopes between aragonite and aqueous Ca2+ decreases with increasing precipitation rates. The large enrichment of 18O vs. 16O isotopes in carbonates is related to the strong bond of oxygen to the small and highly charged C4+-ion. In contrast equilibrium isotopic fractionation between solution and calcite or vaterite is nearly zero as the Ca-O bond length is similar for calcite, vaterite and the hydrated Ca. Aragonite incorporates preferentially the lighter 40Ca isotope as it has very large Ca-O bonds in comparison to the hydrated Ca. At the crystal surface the lighter 40Ca isotopes are preferentially incorporated as dehydration and diffusion of lighter isotopes are faster. Consequently, the surface becomes enriched in

  15. The Isotopic Composition of Cosmic-Ray Iron and Nickel

    NASA Technical Reports Server (NTRS)

    Wiedenbeck, M.; Binns, W.; Christian, E.; Cummings, A.; George, J.; Hink, P.; Klarmann, J.; Leske, R.; Lijowski, M.; Mewaldt, R.; Stone, E.; Rosenvinge, T. von

    2000-01-01

    Observations from the Cosmic Ray Isotope Spectrometer (CRIS) on ACE have been used to derive contraints on the locations, physical conditions, and time scales for cosmic-ray acceleration and transport.

  16. Isotopic composition of Lake Agassiz-Ojibway water just prior to final drainage

    NASA Astrophysics Data System (ADS)

    Hillaire-Marcel, C.; Helie, J.; McKay, J.; Lalonde, A.

    2006-12-01

    Controversies persist with respect to the impact of the final drainage of Lake Agassiz-Ojibway on the thermohaline circulation of the North Atlantic, some 8.4 ka ago. The lack of response of planktic foraminifer isotope records, off Hudson Strait (i.e., at the outlet of the drainage channel) constitutes one of the most puzzling elements in this debate. However, data on the isotopic composition of drainage waters are needed to estimate the response of the 18-O-salinity relationship in NW Atlantic surface waters. In the literature, a large array of isotopic compositions have been suggested, notably for modeling experiment purposes. Scattered information about the isotopic composition of Lake Agassiz water does exist. It includes isotopic measurements of pore waters of lacustrine sediments [1], analyses of oxygen isotopes in cellulose from algal or plant remains [2], and stable isotope compositions of concretions from varves [3]. Whereas, relatively low oxygen isotope values (apx. -25 per mil vs. VSMOW) are inferred for Lake Agassiz waters during cold pulses of the deglaciation, most data suggest much higher values during the final stages of Lake Agassiz-Ojiway, just prior to its drainage. Calcareous concretions from Lake Ojibway varves (not necessarily contemporaneous to the lacustrine stage) yielded oxygen isotope compositions of about -10 per mil (vs. VPDB), suggesting values as high as -14 per mil (vs. VSMOW) for pore waters (assuming a 0-4 degrees C temperature range). Similar high values (as high as -8 per mil vs. VSMOW [1]) were also estimated from pore water analyses of contemporaneous Lake Agassiz sediments. Here, we used a core raised from Eastern Hudson Bay, off Great Whale River, to further document isotopic compositions of the lake waters prior to their drainage into the North Atlantic. The 7.40 m long core has an apx. 1.3 m-thick lacustrine layer at its base, including the drainage sub- layer. It is overlain by Tyrrell Sea clays. Scarce valves of Candona

  17. The isotopic composition of cosmic-ray calcium

    NASA Technical Reports Server (NTRS)

    Wiedenbeck, M. E.; George, J. S.; Binns, W. R.; Christian, E. R.; Cummings, A. C.; Davis, A. J.; Israel, M. H.; Leske, R. A.; Mewaldt, R. A.; Stone, E. C.; Rosenvinge, T. T. von

    2001-01-01

    We find that the relative abundance of cosmic ray calcium isotopes in the cosmic-ray source are very similar to those found in solar-system material, in spite of the fact that different types of stars are thought to be responsible for producing these two isotopes. This observation is consistent with the view that cosmic rays are derived from a mixed sample of interstellar matter.

  18. Controls on ostracod valve geochemistry: Part 2. Carbon and oxygen isotope compositions

    NASA Astrophysics Data System (ADS)

    Decrouy, Laurent; Vennemann, Torsten Walter; Ariztegui, Daniel

    2011-11-01

    The stable carbon and oxygen isotope compositions of fossil ostracods are powerful tools to estimate past environmental and climatic conditions. The basis for such interpretations is that the calcite of the valves reflects the isotopic composition of water and its temperature of formation. However, calcite of ostracods is known not to form in isotopic equilibrium with water and different species may have different offsets from inorganic precipitates of calcite formed under the same conditions. To estimate the fractionation during ostracod valve calcification, the oxygen and carbon isotope compositions of 15 species living in Lake Geneva were related to their autoecology and the environmental parameters measured during their growth. The results indicate that: (1) Oxygen isotope fractionation is similar for all species of Candoninae with an enrichment in 18O of more than 3‰ relative to equilibrium values for inorganic calcite. Oxygen isotope fractionation for Cytheroidea is less discriminative relative to the heavy oxygen, with enrichments in 18O for these species of 1.7 to 2.3‰. Oxygen isotope fractionations for Cyprididae are in-between those of Candoninae and Cytheroidea. The difference in oxygen isotope fractionation between ostracods and inorganic calcite has been interpreted as resulting from a vital effect. (2) Comparison with previous work suggests that oxygen isotope fractionation may depend on the total and relative ion content of water. (3) Carbon isotope compositions of ostracod valves are generally in equilibrium with DIC. The specimens' δ 13C values are mainly controlled by seasonal variations in δ 13C DIC of bottom water or variation thereof in sediment pore water. (4) Incomplete valve calcification has an effect on carbon and oxygen isotope compositions of ostracod valves. Preferential incorporation of CO32- at the beginning of valve calcification may explain this effect. (5) Results presented here as well as results from synthetic carbonate

  19. Analysis of the site-specific carbon isotope composition of propane by gas source isotope ratio mass spectrometer

    NASA Astrophysics Data System (ADS)

    Piasecki, Alison; Sessions, Alex; Lawson, Michael; Ferreira, A. A.; Neto, E. V. Santos; Eiler, John M.

    2016-09-01

    Site-specific isotope ratio measurements potentially provide valuable information about the formation and degradation of complex molecules-information that is lost in conventional bulk isotopic measurements. Here we discuss the background and possible applications of such measurements, and present a technique for studying the site-specific carbon isotope composition of propane at natural abundance based on mass spectrometric analysis of the intact propane molecule and its fragment ions. We demonstrate the feasibility of this approach through measurements of mixtures of natural propane and propane synthesized with site-specific 13C enrichment, and we document the limits of precision of our technique. We show that mass balance calculations of the bulk δ13C of propane based on our site-specific measurements is generally consistent with independent constraints on bulk δ13C. We further demonstrate the accuracy of the technique, and illustrate one of its simpler applications by documenting the site-specific carbon isotope signature associated with gas phase diffusion of propane, confirming that our measurements conform to the predictions of the kinetic theory of gases. This method can be applied to propane samples of moderate size (tens of micromoles) isolated from natural gases. Thus, it provides a means of studying the site-specific stable isotope systematics of propane at natural isotope abundances on sample sizes that are readily recovered from many natural environments. This method may also serve as a model for future techniques that apply high-resolution mass spectrometry to study the site-specific isotopic distributions of larger organic molecules, with potential applications to biosynthesis, forensics and other geochemical subjects.

  20. The Sr isotope composition of the world ocean, marginal and inland seas: Implications for the Sr isotope stratigraphy

    NASA Astrophysics Data System (ADS)

    Kuznetsov, A. B.; Semikhatov, M. A.; Gorokhov, I. M.

    2012-11-01

    We studied the Sr isotope composition of shells of modern shallow-water mollusks and coral fragments. Twenty five of the studied samples were collected in beach zones of open oceans and marginal seas; twelve and eight additional samples are from saline and freshened inland seas respectively. The 87Sr/86Sr ratio in samples from the Atlantic, Indian, and Pacific oceans and their marginal seas corresponds on average to 0.709202 ± 0.000003 and coincides with the average ratio in the standard USGS EN-1 sample. The average 87Sr/86Sr ratio in inner parts of evaporite subbasins of the Mediterranean and Red seas is identical to that of the oceanic water. In shells of shallow-water mollusks from the Black Sea and Sea of Azov, where the degree of seawater dilution by riverine runoff is as high as 50 to 70%, the 87Sr/86Sr ratio is lower than that in the oceans by only a value of 0.00002 on average. As oceanic waters penetrated into these freshwater basins no earlier than in the Holocene, we conclude that the Sr isotopic equilibration with the oceanic water is realized very rapidly in the epicontinental seas even under conditions of restricted water exchange with the World Ocean. The established uniformity of the Sr isotope composition in all geographic types of currently existing sea basins open to the World Ocean proves the efficiency of the Sr isotope stratigraphy in correlation of contemporaneous chemogenic sediments.

  1. The stable hydrogen isotopic composition of sedimentary plant waxes as quantitative proxy for rainfall in the West African Sahel

    NASA Astrophysics Data System (ADS)

    Niedermeyer, Eva M.; Forrest, Matthew; Beckmann, Britta; Sessions, Alex L.; Mulch, Andreas; Schefuß, Enno

    2016-07-01

    Various studies have demonstrated that the stable hydrogen isotopic composition (δD) of terrestrial leaf waxes tracks that of precipitation (δDprecip) both spatially across climate gradients and over a range of different timescales. Yet, reconstructed estimates of δDprecip and corresponding rainfall typically remain largely qualitative, due mainly to uncertainties in plant ecosystem net fractionation, relative humidity, and the stability of the amount effect through time. Here we present δD values of the C31n-alkane (δDwax) from a marine sediment core offshore the Northwest (NW) African Sahel covering the past 100 years and overlapping with the instrumental record of rainfall. We use this record to investigate whether accurate, quantitative estimates of past rainfall can be derived from our δDwax time series. We infer the composition of vegetation (C3/C4) within the continental catchment area by analysis of the stable carbon isotopic composition of the same compounds (δ13Cwax), calculated a net ecosystem fractionation factor, and corrected the δDwax time series accordingly to derive δDprecip. Using the present-day relationship between δDprecip and the amount of precipitation in the tropics, we derive quantitative estimates of past precipitation amounts. Our data show that (a) vegetation composition can be inferred from δ13Cwax, (b) the calculated net ecosystem fractionation represents a reasonable estimate, and (c) estimated total amounts of rainfall based on δDwax correspond to instrumental records of rainfall. Our study has important implications for future studies aiming to reconstruct rainfall based on δDwax; the combined data presented here demonstrate that it is feasible to infer absolute rainfall amounts from sedimentary δDwax in tandem with δ13Cwax in specific depositional settings.

  2. Oxygen isotopic composition of relict olivine grains in cosmic spherules: Links to chondrules from carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Rudraswami, N. G.; Prasad, M. Shyam; Nagashima, K.; Jones, R. H.

    2015-09-01

    Most olivine relict grains in cosmic spherules selected for the present study are pristine and have not been disturbed during their atmospheric entry, thereby preserving their chemical, mineralogical and isotopic compositions. In order to understand the origin of the particles, oxygen isotope compositions of relict olivine grains in twelve cosmic spherules collected from deep sea sediments of the Indian Ocean were studied using secondary ion mass spectrometry. Most of the data lie close to the CCAM (Carbonaceous Chondrite Anhydrous Mineral) line, with Δ17O ranging from -5‰ to 0‰. The data overlap oxygen isotopic compositions of chondrules from carbonaceous chondrites such as CV, CK, CR and CM, which suggests that chondrules from carbonaceous chondrites are the source of relict grains in cosmic spherules. Chemical compositions of olivine in cosmic spherules are also very similar to chondrule olivine from carbonaceous chondrites. Several olivine relict grains in three cosmic spherules are 16O-rich (Δ17O -21.9‰ to -18.7‰), similar to oxygen isotopic compositions observed in calcium aluminum rich inclusions (CAIs), amoeboid olivine aggregates (AOAs), and some porphyritic chondrules from carbonaceous chondrites. These grains appear to have recorded the initial oxygen isotopic composition of the inner solar nebula. Three olivine grains from two cosmic spherules have δ18O values >+20‰, which could be interpreted as mixing with stratospheric oxygen during atmospheric entry.

  3. Trihalomethanes formed from natural organic matter isolates: Using isotopic and compositional data to help understand sources

    USGS Publications Warehouse

    Bergamaschi, B.A.; Fram, M.S.; Fujii, R.; Aiken, G.R.; Kendall, C.; Silva, S.R.

    2000-01-01

    Over 20 million people drink water from the Sacramento-San Joaquin Delta despite problematic levels of natural organic matter (NOM) and bromide in Delta water, which can form trihalomethanes (THMs) during the treatment process. It is widely believed that NOM released from Delta peat islands is a substantial contributor to the pool of THM precursors present in Delta waters. Dissolved NOM was isolated from samples collected at five channel sites within the Sacramento-San Joaquin Rivers and Delta, California, USA, and from a peat island agricultural drain. To help understand the sources of THM precursors, samples were analyzed to determine their chemical and isotopic composition, their propensity to form THMs, and the isotopic composition of the THMs. The chemical composition of the isolates was quite variable, as indicated by significant differences in carbon-13 nuclear magnetic resonance spectra and carbon-to-nitrogen concentration ratios. The lowest propensity to form THMs per unit of dissolved organic carbon was observed in the peat island agricultural drain isolate, even though it possessed the highest fraction of aromatic material and the highest specific ultraviolet absorbance. Changes in the chemical and isotopic composition of the isolates and the isotopic composition of the THMs suggest that the source of the THMs precursors was different between samples and between isolates. The pattern of variability in compositional and isotopic data for these samples was not consistent with simple mixing of river- and peat-derived organic material.

  4. Measurements of the isotopic composition of ice and vapor above a tropical convective system

    NASA Astrophysics Data System (ADS)

    O'Brien, A.; Hanisco, T. F.; Sayres, D. S.; St Clair, J.; Smith, J. B.; Weinstock, E. M.; Anderson, J.

    2011-12-01

    We present observations of the isotopic composition of condensed and vapor water in the lower tropical tropopause layer (TTL) above a large summertime tropical convective system obtained by the Hoxotope and ICOS isotope instruments flown on the NASA WB-57 during TC4. A simple ice isotopic physics model is used in conjunction with our observational data to determine the origin of the condensed phase encountered above the cloud top. Regions of ice that are characteristic of both convective lofting, where the ice is isotopically heavier than the surroundings, and in situ condensation, where the ice shows little difference in isotopic composition with respect to the vapor, are encountered above the convective cell with convective lofting being the dominant mechanism by which water is transported to this altitude. While ice lofting is an important component of water transport models in the TTL, the isotopic composition of ice has been a relatively unconstrained parameter. Observations of condensed isotopes coupled with the vertical profile of vapor in the summertime TTL suggests that there is a seasonal variation in convective timescales that needs to be accounted for in convectively-influenced trajectory models describing the transport of water in the TTL.

  5. Normal variations in the isotopic composition of metabolically relevant transition metals in human blood

    NASA Astrophysics Data System (ADS)

    Van Heghe, L.; Cloquet, C.; Vanhaecke, F.

    2012-04-01

    Cu, Fe and Zn are transition metals with great catalytic, structural and regulating importance in the human body. Hence, an aberrant metabolism of these elements can have serious implications on the health of a person. It is assumed that, due to differences in isotope fractionation, the isotopic composition of these elements in whole blood of patients can be different from that in blood of healthy subjects. Therefore, isotopic analysis of the element affected by the disease can be a promising approach for early diagnosis. A method for isotopic analysis of Cu, Fe and Zn in human whole blood was developed. The simultaneous chromatographic isolation of these elements and the conditions for isotope ratio measurement via multi-collector ICP - mass spectrometry (MC-ICP-MS) were optimized. So far, only whole blood of supposedly healthy volunteers (reference population) was analyzed. Results for Fe confirmed the known differences in isotopic composition between male and female blood. It is also shown that other parameters can have influence as well, e.g., the isotopic composition of Zn seems to be governed by the diet.

  6. Antimony isotopic composition in river waters affected by ancient mining activity.

    PubMed

    Resongles, Eléonore; Freydier, Rémi; Casiot, Corinne; Viers, Jérôme; Chmeleff, Jérôme; Elbaz-Poulichet, Françoise

    2015-11-01

    In this study, antimony (Sb) isotopic composition was determined in natural water samples collected along two hydrosystems impacted by historical mining activities: the upper Orb River and the Gardon River watershed (SE, France). Antimony isotope ratio was measured by HG-MC-ICP-MS (Hydride Generation Multi-Collector Inductively Coupled Plasma Mass Spectrometer) after a preconcentration and purification step using a new thiol-cellulose powder (TCP) procedure. The external reproducibility obtained for δ(123)Sb measurements of our in-house Sb isotopic standard solution and a certified reference freshwater was 0.06‰ (2σ). Significant isotopic variations were evident in surface waters from the upper Orb River (-0.06‰≤δ(123)Sb≤+0.11‰) and from the Gardon River watershed (+0.27‰≤δ(123)Sb≤+0.83‰). In particular, streams that drained different former mining sites exploited for Sb or Pb-Zn exhibited contrasted Sb isotopic signature, that may be related to various biogeochemical processes occurring during Sb transfer from rocks, mine wastes and sediments to the water compartment. Nevertheless, Sb isotopic composition appeared to be stable along the Gardon River, which might be attributed to the conservative transport of Sb at distance from mine-impacted streams, due to the relative mobile behavior of Sb(V) in natural oxic waters. This study suggests that Sb isotopic composition could be a useful tool to track pollution sources and/or biogeochemical processes in hydrologic systems. PMID:26452900

  7. The stable Cr isotopic compositions of chondrites and silicate planetary reservoirs

    NASA Astrophysics Data System (ADS)

    Schoenberg, Ronny; Merdian, Alexandra; Holmden, Chris; Kleinhanns, Ilka C.; Haßler, Kathrin; Wille, Martin; Reitter, Elmar

    2016-06-01

    The depletion of chromium in Earth's mantle (∼2700 ppm) in comparison to chondrites (∼4400 ppm) indicates significant incorporation of chromium into the core during our planet's metal-silicate differentiation, assuming that there was no significant escape of the moderately volatile element chromium during the accretionary phase of Earth. Stable Cr isotope compositions - expressed as the ‰-difference in 53Cr/52Cr from the terrestrial reference material SRM979 (δ53/52CrSRM979 values) - of planetary silicate reservoirs might thus yield information about the conditions of planetary metal segregation processes when compared to chondrites. The stable Cr isotopic compositions of 7 carbonaceous chondrites, 11 ordinary chondrites, 5 HED achondrites and 2 martian meteorites determined by a double spike MC-ICP-MS method are within uncertainties indistinguishable from each other and from the previously determined δ53/52CrSRM979 value of -0.124 ± 0.101‰ for the igneous silicate Earth. Extensive quality tests support the accuracy of the stable Cr isotope determinations of various meteorites and terrestrial silicates reported here. The uniformity in stable Cr isotope compositions of samples from planetary silicate mantles and undifferentiated meteorites indicates that metal-silicate differentiation of Earth, Mars and the HED parent body did not cause measurable stable Cr isotope fractionation between these two reservoirs. Our results also imply that the accretionary disc, at least in the inner solar system, was homogeneous in its stable Cr isotopic composition and that potential volatility loss of chromium during accretion of the terrestrial planets was not accompanied by measurable stable isotopic fractionation. Small but reproducible variations in δ53/52CrSRM979 values of terrestrial magmatic rocks point to natural stable Cr isotope variations within Earth's silicate reservoirs. Further and more detailed studies are required to investigate whether silicate

  8. Isotope composition of iron delivered to the oceans by intertropical rivers: The Amazon River Basin case

    NASA Astrophysics Data System (ADS)

    Poitrasson, F.; Vieira, L. C.; Seyler, P.; dos Santos Pinheiro, G. M.; Mulholland, D. S.; Ferreira Lima, B. A.; Bonnet, M.; Martinez, J.; Prunier, J.

    2011-12-01

    Riverborne iron is a notable source for this biogeochemically key element to the oceans. Recent investigations have shown that its isotopic composition may vary significantly in oceanic waters. Hence, a proper understanding of the Fe cycle at the surface of the Earth requires a good characterization of the isotopic composition of its various reservoirs. However, as the database growths, it appears that the isotope composition of the riverborne Fe delivered to the oceans may be more varied than initially thought, in agreement with inferences from soil studies from different climatic contexts. It is therefore important to compare major rivers from different latitudes. We focused our attention on the Amazon River and its tributaries that represent ca. 20% of the freshwater delivered to the oceans by world rivers. Preliminary experiments suggest that water filtration may induce biases in stable Fe isotope composition. Therefore, we worked first on bulk waters, sampled during multidisciplinary field campaigns on the Amazon River and its tributaries, including the Solimoes, Negro, Madeira and Tapajos Rivers. Besides a complete sample physical-chemical characterization, Fe isotope determinations were conduced after water sample mineralization, iron purification and MC-ICP-MS analysis. Our first results reveal that most bulk water samples cluster close to the continental crust value (0.1% δ57FeIRMM-14) with an overall range of 0.2%. This is consistent with the restricted range found in lateritic soils elsewhere that represent 80% of the Amazon basin surface. Only black water rivers flowing over the podzols of the northern portion of the Amazon basin tend to show lighter isotopic compositions, down to -0.18%. However, sediment analyses suggest that this light Fe isotopic is lost through sedimentation on the river bed, thereby leading the waters to have Fe isotope compositions remaining close to that of the continental crust. This constant isotopic signature holds whatever

  9. The carbon isotope composition of ancient CO2 based on higher-plant organic matter.

    PubMed

    Gröcke, Darren R

    2002-04-15

    Carbon isotope ratios in higher-plant organic matter (delta(13)C(plant)) have been shown in several studies to be closely related to the carbon isotope composition of the ocean-atmosphere carbon reservoir, and, in particular, the isotopic composition of CO(2). These studies have primarily been focused on geological intervals in which major perturbations occur in the oceanic carbon reservoir, as documented in organic carbon and carbonates phases (e.g. Permian-Triassic and Triassic-Jurassic boundary, Early Toarcian, Early Aptian, Cenomanian-Turonian boundary, Palaeocene-Eocene Thermal Maximum (PETM)). All of these events, excluding the Cenomanian-Turonian boundary, record negative carbon isotope excursions, and many authors have postulated that the cause of such excursions is the massive release of continental-margin marine gas-hydrate reservoirs (clathrates). Methane has a very negative carbon isotope composition (delta(13)C, ca. 60 per thousand ) in comparison with higher-plant and marine organic matter, and carbonate. The residence time of methane in the ocean-atmosphere reservoir is short (ca. 10 yr) and is rapidly oxidized to CO(2), causing the isotopic composition of CO(2) to become more negative from its assumed background value (delta(13)C, ca. -7 per thousand ). However, to date, only the Early Toarcian, Early Aptian and PETM are well-constrained chronometric sequences that could attribute clathrate release as a viable cause to create such rapid negative delta(13)C excursions. Notwithstanding this, the isotopic analysis of higher-plant organic matter (e.g. charcoal, wood, leaves, pollen) has the ability to (i) record the isotopic composition of palaeoatmospheric CO(2) in the geological record, (ii) correlate marine and non-marine stratigraphic successions, and (iii) confirm that oceanic carbon perturbations are not purely oceanographic in their extent and affect the entire ocean-atmosphere system. A case study from the Isle of Wight, UK, indicates that the

  10. One year observation of water vapour isotopic composition at Ivittuut, Southern Greenland

    NASA Astrophysics Data System (ADS)

    Bonne, Jean-Louis; Masson-Delmotte, Valérie; Delmotte, Marc; Cattani, Olivier; Sodemann, Harald; Risi, Camille

    2013-04-01

    In September 2011, an automatic continuous water vapour isotopic composition monitoring instrument has been installed in the atmospheric station of Ivittuut (61.21° N, 48.17° W), southern Greenland. Precipitation has been regularly sampled on site at event to weekly scales and analysed in our laboratory for isotopic composition. Meteorological parameters (temperature, pressure, relative humidity, wind speed and direction) and atmospheric composition (CO2, CH4, Atmospheric Potential Oxygen) are also continuously monitored at Ivittuut. The meteorological context of our observation period will be assessed by comparison with the local climatology. The water vapour analyser is a Picarro Wavelength Scanned Cavity Ring-Down Spectrometer (WS-CRDS, model L2120i). It is automatically and regularly calibrated on the VSMOW scale using measurements of the isotopic composition of vaporized reference water standards using the Picarro Syringe Delivery Module (SDM). As measurements are sensitive to humidity level, an experimentally estimated calibration response function is used to correct our isotopic measurements. After data treatment, successive isotopic measurements of reference waters have a standard deviation of around 0.35 per mil for δ18O and 2.3 per mil for δD. Our instrumentation protocol and data quality control method will be presented, together with our one year δ18O, δD and d-excess measurements in water vapour and precipitation. The relationship between surface water vapour isotopic composition and precipitation isotopic composition will be investigated based on a distillation model. Specific difficulties linked to our low maintenance remote station will also be discussed. The processes responsible for the synoptic variability of Ivittuut water vapour isotopic composition will be investigated by comparing our observational dataset with (i) atmospheric back-trajectories and (ii) results from an isotopically-enabled atmospheric general circulation model (AGCM

  11. The influence of oxygen exchange between sulfite and water on the oxygen isotope composition of sulfate

    NASA Astrophysics Data System (ADS)

    Müller, I. A.; Brunner, B.

    2012-12-01

    Sulfate does not exchange oxygen with the water under most environmental conditions. Therefore, its oxygen isotope composition serves as an archive of past oxidative sulfur cycling. Studies on the oxygen isotope signature of sulfate produced from reduced sulfur compounds show varying relative contributions of two possible oxygen sources; molecular oxygen and water, and variable isotope fractionations relative to these two compounds. These discrepancies could be due to differences in the production and consumption of sulfuroxy intermediates which exchange oxygen with water. Thereby, the rate of oxygen exchange as well as the rate of oxidation depends on the pH. Studies on the oxygen isotope exchange effects between sulfuroxy intermediates and water and on the oxygen isotope effects during the oxidation of sulfuroxy intermediates are scarce, severely limiting the interpretability of oxygen isotope signatures in sulfate. Sulfite is often considered to be the last/final sulfuroxy intermediate in the oxidation of reduced sulfur compounds to sulfate and may, therefore, be pivotal in shaping the oxygen isotope signature of sulfate. We determined the oxygen isotope equilibrium fractionation between sulfite and water and used the obtained equilibrium value to determine the oxygen isotope effects in abiotic sulfite oxidation experiments. Our results demonstrate that natural variations in the oxygen isotope composition of sulfate produced by oxidative processes can be explained by differences in the interplay of the sulfite oxidation rate and oxygen isotope exchange rate between sulfite and water which both depend on pH conditions and availability of oxidizing agents (e.g. molecular oxygen or ferric iron). Our findings contribute to a more detailed mechanistic understanding of the oxidation of reduced sulfur compounds and underline the importance of sulfite as the final sulfuroxy intermediate in oxidative sulfur cycling.

  12. Genetic relations among basic lavas and ultramafic nodules: Evidence from oxygen isotope compositions

    USGS Publications Warehouse

    Kyser, T.K.; O'Neil, J.R.; Carmichael, I.S.E.

    1982-01-01

    ??18O values of unaltered basic lavas range from 4.9 to 8.3 but different types of basalts are usually restricted to narrow and distinct ranges of isotopic composition. The average ??18O values for Hawaiian tholeiites, mid-ocean ridge tholeiites, and alkali basalts are 5.4, 5.7, and 6.2 permil, respectively. Potassic lavas and andesites tend to be more 18O rich with ??18O values between 6.0 and 8.0 permil. The differences among the oxygen isotopic compositions of most of these lavas can be attributed to partial melting of isotopically distinct sources. The oxygen isotope compositions of the sources may be a function of prior melting events which produce 18O-depleted partial melts and 18O-enriched residues as a consequence of relatively large isotopic fractionations that exist at high temperatures. It is proposed that lavas with relatively low ??18O values are derived from primitive, 18O-depleted sources whereas 18O-rich basalts are produced from refractory sources that have already produced partial melts. High temperature fractionations among silicate liquids and coexisting minerals can be used in conjunction with the oxygen isotope compositions of ultramafic nodules to place constraints on the genetic relations between some nodules and different types of basic lavas. ?? 1982 Springer-Verlag.

  13. Heterogeneous Os isotope compositions in the Kalatongke sulfide deposit, NW China: the role of crustal contamination

    NASA Astrophysics Data System (ADS)

    Gao, Jian-Feng; Zhou, Mei-Fu; Lightfoot, Peter C.; Qu, Wenjun

    2012-10-01

    Re-Os isotope compositions of mantle-derived magmas are highly sensitive to crustal contamination because the crust and mantle have very different Os isotope compositions. Crustal contamination may trigger S saturation and thus the formation of magmatic Ni-Cu-(PGE) sulfide deposits. The ˜287-Ma Kalatongke norite intrusion of NW China are hosted in carboniferous tuffaceous rocks and contain both disseminated and massive sulfide mineralization. The Re-Os isotope compositions in the intrusion are highly variable. Norite and massive sulfide ores have γ Os values ranging from +59 to +160 and a Re-Os isochron age of 239 ± 51 Ma, whereas disseminated sulfide ores have γ Os values from +117 to +198 and a Re-Os isochron age of 349 ± 34 Ma. The variability of Os isotope compositions can be explained as the emplacement of two distinct magma pulses. Massive sulfide ores and barren norite in the intrusion formed from the same magma pulse, whereas the disseminated sulfide ores with more radiogenic Os isotopes formed from another magma pulse which underwent different degrees of crustal contamination. Re-Os isotopes may not be suitable for dating sulfide-bearing intrusions that underwent variable degrees of crustal contamination to form magmatic sulfide deposits.

  14. Coupled isotopes of plant wax and hemicellulose markers record information on relative humidity and isotopic composition of precipitation

    NASA Astrophysics Data System (ADS)

    Tuthorn, M.; Zech, R.; Ruppenthal, M.; Oelmann, Y.; Kahmen, A.; del Valle, H. F.; Eglinton, T.; Zech, M.

    2015-02-01

    The δ2H isotopic composition of leaf waxes is used increasingly for paleohydrological and -climate reconstructions. However, it is challenging to disentangle past changes in the isotopic composition of precipitation and changes in evapotranspirative enrichment of leaf water. We analyzed δ2H on n-alkanes and fatty acids in topsoils along a climate transect in Argentina, for which we had previously measured δ18O on plant-derived sugars. Our results indicate that leaf wax biomarker δ2H values (δ2Hlipids) primarily reflect δ2Hsource water (precipitation), but are modulated by evapotranspirative enrichment. A mechanistic model is able to produce the main trends in δ2Hlipids along the transect, but seems to slightly underestimate evapotranspirative enrichment in arid regions and overestimate it in grass-dominated ecosystems. Furthermore, the (i) coupling of the δ2Hlipid and δ18Osugar biomarker results and (ii) application of biosynthetic fractionation factors allows calculating the δ2H-δ18O isotopic composition of leaf water along the transect. This also yields the deuterium excess (d excess) of leaf water, which mainly reflects evapotranspirative enrichment, and can be used to model relative air humidity (RH). The high correlation of modeled (reconstructed based on biomarker results) and measured RH, as well as the good agreement between modeled and actual δ2H and δ18O of precipitation along the transect lends support to the coupled δ2Hlipid and δ18Osugar biomarker approach for future paleoclimate research.

  15. The influence of kinetics on the oxygen isotope composition of calcium carbonate

    NASA Astrophysics Data System (ADS)

    Watkins, James M.; Nielsen, Laura C.; Ryerson, Frederick J.; DePaolo, Donald J.

    2013-08-01

    Paleotemperature reconstructions rely on knowledge of the equilibrium separation of oxygen isotopes between aqueous solution and calcium carbonate. Although oxygen isotope separation is expected on theoretical grounds, the temperature-dependence remains uncertain because other factors, such as slow exchange of isotopes between dissolved CO2-species and water, can obscure the temperature signal. This is problematic for crystal growth experiments on laboratory timescales and for interpreting the oxygen isotope composition of crystals formed in natural settings. We present results from experiments in which inorganic calcite is precipitated in the presence of 0.25 μM dissolved bovine carbonic anhydrase (CA). The presence of dissolved CA accelerates oxygen isotope equilibration between the dissolved carbon species CO2, H2CO3, HCO3-, CO32- and water, thereby eliminating this source of isotopic disequilibrium during calcite growth. The experimental results allow us to isolate, for the first time, kinetic oxygen isotope effects occurring at the calcite-water interface. We present a framework of ion-by-ion growth of calcite that reconciles our new measurements with measurements of natural cave calcites that are the best candidate for having precipitated under near-equilibrium conditions. Our findings suggest that isotopic equilibrium between calcite and water is unlikely to have been established in laboratory experiments or in many natural settings. The use of CA in carbonate precipitation experiments offers new opportunities to refine oxygen isotope-based geothermometers and to interrogate environmental variables other than temperature that influence calcite growth rates.

  16. Assessment of shock effects on amphibole water contents and hydrogen isotope compositions: 1. Amphibolite experiments

    NASA Astrophysics Data System (ADS)

    Minitti, Michelle E.; Rutherford, Malcolm J.; Taylor, Bruce E.; Dyar, M. Darby; Schultz, Peter H.

    2008-02-01

    Kaersutitic amphiboles found within a subset of the Martian meteorites have low water contents and variably heavy hydrogen isotope compositions. In order to assess if impact shock-induced devolatilization and hydrogen isotope fractionation were determining factors in these water and isotopic characteristics of the Martian kaersutites, we conducted impact shock experiments on samples of Gore Mountain amphibolite in the Ames Vertical Gun Range (AVGR). A parallel shock experiment conducted on an anorthosite sample indicated that contamination of shocked samples by the AVGR hydrogen propellant was unlikely. Petrographic study of the experimental amphibolite shock products indicates that only ˜ 10% of the shock products experienced levels of damage equivalent to those found in the most highly shocked kaersutite-bearing Martian meteorites (30-35 GPa). Ion microprobe studies of highly shocked hornblende from the amphibolite exhibited elevated water contents (ΔH 2O ˜ 0.1 wt.%) and enriched hydrogen isotope compositions (Δ D ˜ + 10‰) relative to unshocked hornblende. Water and hydrogen isotope analyses of tens of milligrams of unshocked, moderately shocked, and highly shocked hornblende samples by vacuum extraction/uranium reduction and isotope ratio mass spectrometry (IRMS), respectively, are largely consistent with analyses of single grains from the ion microprobe. The mechanisms thought to have produced the excess water in most of the shocked hornblendes are shock-induced reduction of hornblende Fe and/or irreversible adsorption of hydrogen. Addition of the isotopically enriched Martian atmosphere to the Martian meteorite kaersutites via these mechanisms could explain their enriched and variable isotopic compositions. Alternatively, regrouping the water extraction and IRMS analyses on the basis of isotopic composition reveals a small, but consistent, degree of impact-induced devolatilization (˜ 0.1 wt.% H 2O) and H isotope enrichment (Δ D ˜ + 10

  17. Chromium isotope composition of reducing and anoxic sediments from the Peru Margin and Cariaco Basin

    NASA Astrophysics Data System (ADS)

    Gueguen, B.; Planavsky, N.; Wang, X.; Algeo, T. J.; Peterson, L. C.; Reinhard, C. T.

    2014-12-01

    Chromium isotope systematics in marine sediments are now being used as a new redox proxy of the modern and ancient Earth's surface. Chromium is primarily delivered to the oceans by riverine inputs through weathering of Cr(III)-rich minerals present in the continental crust and oxidation of insoluble Cr(III) to soluble Cr(VI) species. Since oxidation-reduction reactions fractionate Cr isotopes whereby oxidized Cr(VI) species are preferentially enriched in heavy Cr isotopes, the Cr isotope composition of marine sediments may be useful tracers of redox conditions at the Earth's surface through geological time. Chromium is quantitatively removed in organic-rich sediments where reducing conditions prevail and promote reduction of Cr(VI) to Cr(III), and thus, these sediments should capture the ambient seawater Cr isotope composition. However, the isotopic composition of modern organic-rich sediments is poorly documented so far, and this step is essential for further modeling the global oceanic Cr isotope mass balance and assessing the effects of sedimentation and post-depositional processes on the marine Cr isotopes archive. In this study, we have characterized modern marine organic-rich sediments for their Cr isotope composition (δ53/52Cr) from two different settings, the Peru margin upwelling zone and the anoxic Cariaco Basin (Venezuela). Chromium isotopes were measured on a MC-ICP-MS (Nu Plasma) using a double-spike correction method. The authigenic fraction of shallow samples from the Peru margin sedimentary sequence with a high Total Organic Carbon (TOC) content (>10 wt%) yield an average δ53/52Crauthigenic value of +0.67 ±0.05 ‰ (2sd). However, although this value is close to the seawater value (Atlantic Ocean) and to Cariaco basin sediments (~ +0.6 ‰), reducing sediments from the Peru margin are on average isotopically slightly heavier, especially in samples having a low authigenic fraction and a low TOC content (δ53/52Crauthigenic values up to +1.30

  18. Natural variations in calcium isotope composition as a monitor of bone mineral balance in humans.

    NASA Astrophysics Data System (ADS)

    Skulan, J.; Anbar, A.; Thomas, B.; Smith, S.

    2004-12-01

    The skeleton is the largest reservoir of calcium in the human body and is responsible for the short term control of blood levels of this element. Accurate measurement of changes in bone calcium balance is critical to understanding how calcium metabolism responds to physiological and environmental changes and, more specifically, to diagnosing and evaluating the effectiveness of treatments for osteoporosis and other serious calcium-related disorders. It is very difficult to measure bone calcium balance using current techniques, however, because these techniques rely either on separate estimates of bone resorption and formation that are not quantitatively comparable, or on complex and expensive studies of calcium kinetics using administered isotopic tracers. This difficulty is even more apparent and more severe for measurements of short-term changes in bone calcium balance that do not produce detectable changes in bone mineral density. Calcium isotopes may provide a novel means of addressing this problem. The foundation of this isotope application is the ca. 1.3 per mil fractionation of calcium during bone formation, favoring light calcium in the bone. This fractionation results in a steady-state isotopic offset between calcium in bone and calcium in soft tissues, blood and urine. Perturbations to this steady state due to changes in the net formation or resorption of bone should be reflected in changes in the isotopic composition of soft tissues and fluids. Here we present evidence that easily detectable shifts in the natural calcium isotope composition of human urine rapidly reflect changes in bone calcium balance. Urine from subjects in a 17-week bed rest study was analyzed for calcium isotopic composition. Bed rest promotes net resorption of bone, shifting calcium from bone to soft tissues, blood and urine. The calcium isotope composition of patients in this study shifted toward lighter values during bed rest, consistent with net resorption of isotopically

  19. Hafnium and neodymium isotope composition of seawater and filtered particles from the Southern Ocean

    NASA Astrophysics Data System (ADS)

    Stichel, T.; Frank, M.; Haley, B. A.; Rickli, J.; Venchiarutti, C.

    2009-12-01

    Radiogenic hafnium (Hf) and neodymium (Nd) isotopes have been used as tracers for past continental weathering regimes and ocean circulation. To date, however, there are only very few data available on dissolved Hf isotope compositions in present-day seawater and there is a complete lack of particulate data. During expedition ANTXXIV/3 (February to April 2008) we collected particulate samples (> 0.8 µm), which were obtained by filtrations of 270-700 liters of water. The samples were separated from the filters, completely dissolved, and purified for Nd and Hf isotope determination by TIMS and MC-ICPMS, respectively. In addition, we collected filtered (0.45 µm) seawater samples (20-120 liters) to determine the dissolved isotopic composition of Hf and Nd. The Hf isotope composition of the particulate fraction in the Drake Passage ranged from 0 to -28 ɛHf and is thus similar to that observed in core top sediments from the entire Southern Ocean in a previous study. The most unradiogenic and isotopically homogenous Hf isotope compositions in our study were found near the Antarctic Peninsula. Most of the stations north of the Southern Antarctic Circumpolar Front (SACC) show a large variation in ɛHf between 0 and -23 within the water column of one station and between the stations. The locations at which these Hf isotope compositions were measured are mostly far away from the potential source areas. Nd, in contrast, was nearly absent throughout the entire sample set and the only measurable ɛNd data ranged from 0 to -7, which is in good agreement with the sediment data in that area. The dissolved seawater isotopic compositions of both Hf and Nd show only minor variance (ɛHf = 4.2 to 4.7 and ɛNd = -8.8 to -7.6, respectively). These patterns in Hf isotopes and the nearly complete absence of Nd indicates that the particulate fraction does not contain a lot of terrigeneous material but is almost entirely dominated by biogenic opal. The homogenous and relatively radiogenic

  20. Isotopic composition of water of crystallisation of sulfates of Permian-Triassic age, Eastern Alps, Austria

    NASA Astrophysics Data System (ADS)

    Bojar, Ana-Voica; Halas, Stanislaw; Trembaczowski, Andrzej; Bojar, Hans-Peter

    2016-04-01

    The investigated sulfates as gypsum and polyhalite were selected from various gypsum and halite rich deposits of the Northern Calcareous Alps and the Central Alpine Mesozoic. The two units of the Eastern Alps are characterised by the presence of Permian-Triassic evaporitic deposits. Crystallisation water of mineral phases was extracted by heating the samples under vacuum. The cryogenically trapped water was subsequently analysed for delta 18O and delta D on a Picarro L2120-i Analyzer. The isotopic compositions were synchronously measured, with a standard deviation better than 0.1 permil. The fractionation factors for both oxygen and hydrogen between brine where the sulfates formed and crystallisation water of sulfates are not temperature dependent. Using the appropriate relationships, we conclude from the calculations that, for gypsum, oxygen and hydrogen isotopic composition of fluid in equilibrium with crystallisation water varied between -16 to -6 permil and between -90 to -25 permil, respectively. The crystallization water of gypsum associated with halite type deposits has heavier isotopic compositions. The isotopic composition of crystallisation water of gypsum points towards reequilibration with a younger meteoric fluid. In contrast, polyhalite crystallisation water show much heavier values between +10 to +11 permil for oxygen and +16 to +19 permil for hydrogen. These values suggest the fact that this water of crystallisation indicates the isotopic composition of brines. The origin of these brines, diagenetic versus later thermal overprint is subject of further investigations. All the measured values plot along a regression line.

  1. Lead content and isotopic composition in submound and recent soils of the Volga Upland

    NASA Astrophysics Data System (ADS)

    Pampura, T. V.; Probst, A.; Ladonin, D. V.; Demkin, V. A.

    2013-11-01

    Literature data on the historical reconstructions of the atmospheric lead deposition in Europe and the isotopic composition of the ores that are potential sources of the anthropogenic lead in the atmospheric deposition in the lower Volga steppes during different time periods have been compiled. The effect of the increasing anthropogenic lead deposition recorded since the Bronze Age on the level of soil contamination has been investigated. For the first time paleosol buried under a burial mound of the Bronze Age has been used as a reference point to assess of the current contamination level. The contents and isotopic compositions of the mobile and total lead have been determined in submound paleosols of different ages and their recent remote and roadside analogues. An increase in the content and fraction of the mobile lead and a shift of its isotopic composition toward less radiogenic values (typical for lead from the recent anthropogenic sources) has been revealed when going from a Bronze-Age paleosol to a recent soil. In the Bronze-Age soil, the isotopic composition of the mobile lead is inherited from the parent rock to a greater extent than in the modern soils, where the lead is enriched with the less radiogenic component. The effect of the anthropogenic component is traced in the analysis of the mobile lead, but it is barely visible for the total lead. An exception is provided by the recent roadside soils characterized by increased contents and the significantly less radiogenic isotopic composition of the mobile and total lead.

  2. The minor sulfur isotope composition of Cretaceous and Cenozoic seawater sulfate

    NASA Astrophysics Data System (ADS)

    Masterson, A. L.; Wing, Boswell A.; Paytan, Adina; Farquhar, James; Johnston, David T.

    2016-06-01

    The last 125 Myr capture major changes in the chemical composition of the ocean and associated geochemical and biogeochemical cycling. The sulfur isotopic composition of seawater sulfate, as proxied in marine barite, is one of the more perplexing geochemical records through this interval. Numerous analytical and geochemical modeling approaches have targeted this record. In this study we extend the empirical isotope record of seawater sulfate to therefore include the two minor sulfur isotopes, 33S and 36S. These data record a distribution of values around means of Δ33S and Δ36S of 0.043 ± 0.016‰ and -0.39 ± 0.15‰, which regardless of δ34S-based binning strategy is consistent with a signal population of values throughout this interval. We demonstrate with simple box modeling that substantial changes in pyrite burial and evaporite sulfate weathering can be accommodated within the range of our observed isotopic values.

  3. Ca-,Al-rich inclusions in the unique chondrite ALH85085 - Petrology, chemistry, and isotopic compositions

    NASA Technical Reports Server (NTRS)

    Kimura, Makoto; El-Goresy, Ahmed; Palme, Herbert; Zinner, Ernst

    1993-01-01

    A comprehensive study is performed for the Ca-,Al-rich inclusions (CAIs) in the unique chondrite ALH85085. The ALH85085 inclusions are smaller (5-80 microns) and more refractory than their counterparts in carbonaceous chondrites. The study includes 42 inclusions for petrography and mineralogy, 15 for bulk major and minor element chemical composition, six for Mg-Al isotopic systematics, 10 for Ca isotopes, nine for Ti isotopes, and six for trace element abundances. In addition, oxygen-isotopic compositions were determined in minerals from a single inclusion. No correlation is found between mineralogy, major element chemistry, and trace element abundances. It is further shown that the high-temperature geochemical behavior of ultrarefractory trace elements is decoupled from that of the major elements Ca and Ti (Ti is correlated with the relatively volatile elements Nb and Yb) implying that perovskite is of only minor importance as carrier of ultrarefractories.

  4. Ca-,Al-rich inclusions in the unique chondrite ALH85085 - Petrology, chemistry, and isotopic compositions

    NASA Astrophysics Data System (ADS)

    Kimura, M.; El Goresy, A.; Palme, H.; Zinner, E.

    1993-05-01

    A comprehensive study is performed for the Ca-,Al-rich inclusions (CAIs) in the unique chondrite ALH85085. The ALH85085 inclusions are smaller (5-80 microns) and more refractory than their counterparts in carbonaceous chondrites. The study includes 42 inclusions for petrography and mineralogy, 15 for bulk major and minor element chemical composition, six for Mg-Al isotopic systematics, 10 for Ca isotopes, nine for Ti isotopes, and six for trace element abundances. In addition, oxygen-isotopic compositions were determined in minerals from a single inclusion. No correlation is found between mineralogy, major element chemistry, and trace element abundances. It is further shown that the high-temperature geochemical behavior of ultrarefractory trace elements is decoupled from that of the major elements Ca and Ti (Ti is correlated with the relatively volatile elements Nb and Yb) implying that perovskite is of only minor importance as carrier of ultrarefractories.

  5. Determination of the hydrogen isotopic compositions of organic materials and hydrous minerals using thermal combustion laser spectroscopy.

    PubMed

    Koehler, Geoff; Wassenaar, Leonard I

    2012-04-17

    Hydrogen isotopic compositions of hydrous minerals and organic materials were measured by combustion to water, followed by optical isotopic analysis of the water vapor by off-axis integrated cavity output spectroscopy. Hydrogen and oxygen isotopic compositions were calculated by numerical integration of the individual isotopologue concentrations measured by the optical spectrometer. Rapid oxygen isotope exchange occurs within the combustion reactor between water vapor and molecular oxygen so that only hydrogen isotope compositions may be determined. Over a wide range in sample sizes, precisions were ±3-4 per mil. This is comparable but worse than continuous flow-isotope ratio mass spectroscopy (CF-IRMS) methods owing to memory effects inherent in water vapor transfer. Nevertheless, the simplicity and reduced cost of this analysis compared to classical IRMS or CF-IRMS methods make this an attractive option to determine the hydrogen isotopic composition of organic materials where the utmost precision or small sample sizes are not needed. PMID:22432837

  6. Clumped Isotope Composition of Cold-Water Corals: A Role for Vital Effects?

    NASA Astrophysics Data System (ADS)

    Spooner, P.; Guo, W.; Robinson, L. F.

    2014-12-01

    Measurements on a set of cold-water corals (mainly Desmophyllum dianthus) have suggested that their clumped isotope composition could serve as a promising proxy for reconstructing paleocean temperatures. Such measurements have also offered support for certain isotope models of coral calcification. However, there are differences in the clumped isotope compositions between warm-water and cold-water corals, suggesting that different kinds of corals could have differences in their biocalcification processes. In order to understand the systematics of clumped isotope variations in cold-water corals more fully, we present clumped isotope data from a range of cold-water coral species from the tropical Atlantic and the Southern Ocean.Our samples were either collected live or recently dead (14C ages < 1,000 yrs) with associated temperature data. They include a total of 11 solitary corals and 1 colonial coral from the Atlantic, and 8 solitary corals from the Southern Ocean. The data indicate that coral clumped isotope systematics may be more complicated than previously thought. For example, for the genus Caryophyllia we observe significant variations in clumped isotope compositions for corals which grew at the same temperature with an apparent negative correlation between Δ47 and δ18O, different to patterns previously observed in Desmophyllum. These results indicate that existing isotope models of biocalcification may not apply equally well to all corals. Clumped isotope vital effects may be present in certain cold-water corals as they are in warm-water corals, complicating the use of this paleoclimate proxy.

  7. Potassium Isotopic Compositions of NIST Potassium Standards and 40Ar/39Ar Mineral Standards

    NASA Technical Reports Server (NTRS)

    Morgan, Leah; Tappa, Mike; Ellam, Rob; Mark, Darren; Higgins, John; Simon, Justin I.

    2013-01-01

    Knowledge of the isotopic ratios of standards, spikes, and reference materials is fundamental to the accuracy of many geochronological methods. For example, the 238U/235U ratio relevant to U-Pb geochronology was recently re-determined [1] and shown to differ significantly from the previously accepted value employed during age determinations. These underlying values are fundamental to accurate age calculations in many isotopic systems, and uncertainty in these values can represent a significant (and often unrecognized) portion of the uncertainty budget for determined ages. The potassium isotopic composition of mineral standards, or neutron flux monitors, is a critical, but often overlooked component in the calculation of K-Ar and 40Ar/39Ar ages. It is currently assumed that all terrestrial materials have abundances indistinguishable from that of NIST SRM 985 [2]; this is apparently a reasonable assumption at the 0.25per mille level (1s) [3]. The 40Ar/39Ar method further relies on the assumption that standards and samples (including primary and secondary standards) have indistinguishable 40K/39K values. We will present data establishing the potassium isotopic compositions of NIST isotopic K SRM 985, elemental K SRM 999b, and 40Ar/39Ar biotite mineral standard GA1550 (sample MD-2). Stable isotopic compositions (41K/39K) were measured by the peak shoulder method with high resolution MC-ICP-MS (Thermo Scientific NEPTUNE Plus), using the accepted value of NIST isotopic SRM 985 [2] for fractionation [4] corrections [5]. 40K abundances were measured by TIMS (Thermo Scientific TRITON), using 41K/39K values from ICP-MS measurements (or, for SRM 985, values from [2]) for internal fractionation corrections. Collectively these data represent an important step towards a metrologically traceable calibration of 40K concentrations in primary 40Ar/39Ar mineral standards and improve uncertainties by ca. an order of magnitude in the potassium isotopic compositions of standards.

  8. Factors that control the stable carbon isotopic composition of methane produced in an anoxic marine sediment

    NASA Technical Reports Server (NTRS)

    Alperin, M. J.; Blair, Neal E.; Albert, D. B.; Hoehler, T. M.; Martens, C. S.

    1993-01-01

    The carbon isotopic composition of methane produced in anoxic marine sediment is controlled by four factors: (1) the pathway of methane formation, (2) the isotopic composition of the methanogenic precursors, (3) the isotope fractionation factors for methane production, and (4) the isotope fractionation associated with methane oxidation. The importance of each factor was evaluated by monitoring stable carbon isotope ratios in methane produced by a sediment microcosm. Methane did not accumulate during the initial 42-day period when sediment contained sulfate, indicating little methane production from 'noncompetitive' substrates. Following sulfate depletion, methane accumulation proceeded in three distinct phases. First, CO2 reduction was the dominant methanogenic pathway and the isotopic composition of the methane produced ranged from -80 to -94 per thousand. The acetate concentration increased during this phase, suggesting that acetoclastic methanogenic bacteria were unable to keep pace with acetate production. Second, acetate fermentation became the dominant methanogenic pathway as bacteria responded to elevated acetate concentrations. The methane produced during this phase was progressively enriched in C-13, reaching a maximum delta(C-13) value of -42 per thousand. Third, the acetate pool experienced a precipitous decline from greater than 5 mM to less than 20 micro-M and methane production was again dominated by CO2 reduction. The delta(C-13) of methane produced during this final phase ranged from -46 to -58 per thousand. Methane oxidation concurrent with methane production was detected throughout the period of methane accumulation, at rates equivalent to 1 to 8 percent of the gross methane production rate. Thus methane oxidation was too slow to have significantly modified the isotopic signature of methane. A comparison of microcosm and field data suggests that similar microbial interactions may control seasonal variability in the isotopic composition of methane

  9. Variation in the terrestrial isotopic composition and atomic weight of argon

    USGS Publications Warehouse

    Böhlke, John Karl

    2014-01-01

    The isotopic composition and atomic weight of argon (Ar) are variable in terrestrial materials. Those variations are a source of uncertainty in the assignment of standard properties for Ar, but they provide useful information in many areas of science. Variations in the stable isotopic composition and atomic weight of Ar are caused by several different processes, including (1) isotope production from other elements by radioactive decay (radiogenic isotopes) or other nuclear transformations (e.g., nucleogenic isotopes), and (2) isotopic fractionation by physical-chemical processes such as diffusion or phase equilibria. Physical-chemical processes cause correlated mass-dependent variations in the Ar isotope-amount ratios (40Ar/36Ar, 38Ar/36Ar), whereas nuclear transformation processes cause non-mass-dependent variations. While atmospheric Ar can serve as an abundant and homogeneous isotopic reference, deviations from the atmospheric isotopic ratios in other Ar occurrences limit the precision with which a standard atomic weight can be given for Ar. Published data indicate variation of Ar atomic weights in normal terrestrial materials between about 39.7931 and 39.9624. The upper bound of this interval is given by the atomic mass of 40Ar, as some samples contain almost pure radiogenic 40Ar. The lower bound is derived from analyses of pitchblende (uranium mineral) containing large amounts of nucleogenic 36Ar and 38Ar. Within this interval, measurements of different isotope ratios (40Ar/36Ar or 38Ar/36Ar) at various levels of precision are widely used for studies in geochronology, water–rock interaction, atmospheric evolution, and other fields.

  10. Clumped isotope composition of cold-water corals: A role for vital effects?

    NASA Astrophysics Data System (ADS)

    Spooner, Peter T.; Guo, Weifu; Robinson, Laura F.; Thiagarajan, Nivedita; Hendry, Katharine R.; Rosenheim, Brad E.; Leng, Melanie J.

    2016-04-01

    The carbonate clumped isotope thermometer is a promising tool for determining past ocean temperatures. It is based on the temperature dependence of rare isotopes 'clumping' into the same carbonate ion group in the carbonate mineral lattice. The extent of this clumping effect is independent of the isotope composition of the water from which carbonate precipitates, providing unique advantages over many other paleotemperature proxies. Existing calibrations of this thermometer in cold-water and warm-water corals suggest clumped isotope 'vital effects' are negligible in cold-water corals but may be significant in warm-water corals. Here, we test the calibration of the carbonate clumped isotope thermometer in cold-water corals with a recently collected and well characterised sample set spanning a range of coral genera (Balanophyllia, Caryophyllia, Dasmosmilia, Desmophyllum, Enallopsammia and Javania). The clumped isotope compositions (Δ47) of these corals exhibit systematic dependences on their growth temperatures, confirming the basis of the carbonate clumped isotope thermometer. However, some cold-water coral genera show Δ47 values that are higher than the expected equilibrium values by up to 0.05‰ (equivalent to underestimating temperature by ∼9 °C) similar to previous findings for some warm-water corals. This finding suggests that the vital effects affecting corals Δ47 are common to both warm- and cold-water corals. By comparison with models of the coral calcification process we suggest that the clumped isotope offsets in these genera are related to the kinetic isotope effects associated with CO2 hydration/hydroxylation reactions in the corals' calcifying fluid. Our findings complicate the use of the carbonate clumped isotope thermometer in corals, but suggest that species- or genus-specific calibrations could be useful for the future application of this paleotemperature proxy.

  11. Elemental composition, isotopes, electrons and positrons in cosmic rays

    NASA Technical Reports Server (NTRS)

    Balasubrahmanyan, V. K.

    1979-01-01

    Papers presented at the 16th International Cosmic Ray Conference, Kyoto, Japan, dealing with the composition of cosmic rays are reviewed. Particular interest is given to data having bearing on nucleosynthesis sites, supernovae, gamma-process, comparison with solar system composition, multiplicity of sources, and the energy dependence of composition.

  12. Fe Isotopic Composition of Presolar SiC Mainstream Grains

    NASA Technical Reports Server (NTRS)

    Tripa, C. E.; Pellin, M. J.; Savina, M. R.; Davis, A. M.; Lewis, R. S.; Clayton, R. N.

    2002-01-01

    Iron isotopic distribution was measured in SiC mainstream grains from the Murchison meteorite by time-of-flight resonance ionization mass spectrometry. All grains exhibit 54Fe depletions of 50 to 200, lower than what are predicted by calculations of s-process nucleosynthesis in AGB stars. Additional information is contained in the original extended abstract.

  13. Magnesium Isotopic Composition of CAIs and Chondrules from CBb Chondrites

    NASA Astrophysics Data System (ADS)

    Gounelle, M.; Young, E. D.; Shahar, A.; Kearsley, A.

    2006-03-01

    We measured magnesium isotope ratios in 17 chondrules and 3 CAIs from the CBb chondrites HH 237 and QUE 94411 by LA-MC-ICPMS. We find no detectable 26Al excesses in the three CAIs and approximately normal (chondritic) d25Mg in CAIs and chondrules.

  14. Determining the oxygen isotope composition of evapotranspiration with eddy covariance

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The oxygen isotope componsition of evapotranspiration (dF) represents an important tracer in the study of biosphere-atmosphere interactions, hydrology, paleoclimate, and carbon cycling. Here we demonstrate direct measurement of dF based on eddy covariance (EC) and tunable diode laser (EC-TDL) techni...

  15. Zirconium isotope constraints on the composition of Theia and current Moon-forming theories

    NASA Astrophysics Data System (ADS)

    Akram, W.; Schönbächler, M.

    2016-09-01

    The giant impact theory is the most widely recognized formation scenario of the Earth's Moon. Giant impact models based on dynamical simulations predict that the Moon acquired a significant amount of impactor (Theia) material, which is challenging to reconcile with geochemical data for O, Si, Cr, Ti and W isotopes in the Earth and Moon. Three new giant impact scenarios have been proposed to account for this discrepancy - hit-and-run impact, impact with a fast-spinning protoEarth and massive impactors - each one reducing the proportion of the impactor in the Moon compared to the original canonical giant impact model. The validity of each theory and their different dynamical varieties are evaluated here using an integrated approach that considers new high-precision Zr isotope measurements of lunar rocks, and quantitative geochemical modelling of the isotopic composition of the impactor Theia. All analysed lunar samples (whole-rock, ilmenite and pyroxene separates) display identical Zr isotope compositions to that of the Earth within the uncertainty of 13 ppm for 96Zr/90Zr (2σ weighted average). This 13 ppm upper limit is used to infer the most extreme isotopic composition that Theia could have possessed, relative to the Earth, for each of the proposed giant impact theories. The calculated Theian composition is compared with the Zr isotope compositions of different solar system materials in order to constrain the source region of the impactor. As a first order approximation, we show that all considered models (including the canonical) are plausible, alleviating the initial requirement for the new giant impact models. Albeit, the canonical and hit-and-run models are the most restrictive, suggesting that the impactor originated from a region close to the Earth. The fast-spinning protoEarth and massive impactor models are more relaxed and increase the allowed impactor distance from the Earth. Similar calculations carried out for O, Cr, Ti and Si isotope data support

  16. Uranium isotope compositions of the basaltic angrite meteorites and the chronological implications for the early Solar System

    PubMed Central

    Brennecka, Gregory A.; Wadhwa, Meenakshi

    2012-01-01

    Events occurring within the first 10 million years of the Solar System’s approximately 4.5 billion-year history, such as formation of the first solids, accretion, and differentiation of protoplanetary bodies, have determined the evolutionary course of our Solar System and the planetary bodies within it. The application of high-resolution chronometers based on short-lived radionuclides is critical to our understanding of the temporal sequence of these critical events. However, to map the relative ages from such chronometers onto the absolute time scale, they must be “anchored” to absolute ages of appropriate meteoritic materials using the high-precision lead–lead (Pb–Pb) chronometer. Previously reported Pb–Pb dates of the basaltic angrite meteorites, some of which have been used extensively as time anchors, assumed a constant 238U/235U ratio (= 137.88). In this work, we report measurements of 238U/235U ratios in several angrites that are distinct from the previously assumed value, resulting in corrections to the Pb–Pb ages of ≥1 million years. There is no resolvable variation in the 238U/235U ratio among the angrite bulk samples or mineral separates, suggesting homogeneity in the U isotopic composition of the angrite parent body. Based on these measurements, we recalculated the Pb–Pb age for the commonly used anchor, the D’Orbigny angrite, to be 4563.37 ± 0.25 Ma. An adjustment to the Pb–Pb age of a time anchor (such as D’Orbigny) requires a corresponding correction to the “model ages” of all materials dated using that anchor and a short-lived chronometer. This, in turn, has consequences for accurately defining the absolute timeline of early Solar System events. PMID:22647606

  17. Isotopic composition of high-activity particles released in the Chernobyl accident

    SciTech Connect

    Osuch, S.; Dabrowska, M.; Jaracz, P.; Kaczanowski, J.; Le Van Kho; Mirowski, S.; Piasecki, E.; Szeflinska, G.; Szeflinski, Z.; Tropilo, J.; )

    1989-11-01

    Gamma spectra were measured and activities of the detected isotopes were analyzed for 206 high-activity particles (hot particles, HPs) found in northeastern Poland after the Chernobyl accident. The isotopic composition of HPs observed in gamma-activity is compared with that of the general fallout and core inventory calculations. Particle formation and a process of depletion in Ru and Cs isotopes are discussed. On the basis of a search performed a year later, some comments on the behavior of HPs in the soil are made.

  18. A large area multi-element telescope for measuring the cosmic ray isotope composition

    NASA Technical Reports Server (NTRS)

    Fisher, A. J.; Ormes, J. F.; Hagen, F. A.

    1974-01-01

    To measure the isotopic composition of cosmic rays up to Fe an instrument is needed with good isotopic resolution and a large exposure. The large geometry needed for a balloon-borne detector has been obtained with large mapped detectors and a trajectory determining spark chamber. The instrument achieves isotopic resolution only for stopping particles. For low charge particles where there is no Cerenkov response the detector works as a multiple dE/dx-Range-Energy detector. For higher charges where scintillator saturation becomes important it becomes a Cerenkov-range measurement.

  19. Copper and Zinc isotope composition of CR, CB and CH-like meteorites.

    NASA Astrophysics Data System (ADS)

    Russell, S.; Zhu, X.; Guo, Y.; Mullane, E.; Gounelle, M.; Mason, T.; Coles, B.

    2003-04-01

    Copper and zinc isotopes have recently been shown to be variable in isotopic composi-tion among terrestrial and extraterrestrial materials [1-3]. For this study, we have se-lected samples (bulk meteorite and chondrule separates) from the CR meteorite clan: Bencubbin (CB), Renazzo (CR2), NWA 801 (CR2), and HaH237 (CH-like). These meteorites were selected because meteorites from this clan have experienced very little alteration since their initial formation [4] and for their extremely high refrac-tory/volatile element ratios. The latter characteristic may allow a test of the correlation observed by [2] between element ratios and Cu isotope composition. Measurements were performed on NHM/IC Micromass Isoprobe and Oxford Nu MC-ICP-MS using techniques described elsewhere [1,5]. Each of the meteorites measured so far for Cu and Zn are isotopically light compared to the terrestrial mantle. This suggests that the terrestrial value may have been altered from the pristine solar system value, or else there were multiple early solar system components. Zinc isotopic com-positions lie on a fractionation line and range from δ66ZnNIST = -1.4±0.1ppm (bulk NWA801) to -1.9±0.1ppm (separated chondrule, NWA 801). Copper isotope compositions vary from δ65CuNIST976 = -1.5±0.1ppm (bulk Renazzo) to -3.1±0.1ppm (separated chondrule, NWA 801). Two chondrules from NWA 801 have differing Cu isotope values (-3.1±0.1 and -2.0±0.1ppm) and both are lighter than the bulk meteorite (-1.9±0.1ppm), suggesting a lack of equilibration with respect to Cu in this meteorite. The light values for the two separated chondrules, compared the bulk meteorite, hints that chondrules may be isotopically lighter than co-existing matrix, metal and sulphides with respect to Cu. The copper isotope compositions are not as isotopically light as expected for the high refractory/volatile element ratio observed in these chondrites. Thus a model to account for the Cu isotopes in chondrites may require greater com

  20. The elemental and isotopic composition of cosmic rays - Silicon to nickel

    NASA Technical Reports Server (NTRS)

    Young, J. S.; Freier, P. S.; Waddington, C. J.; Brewster, N. R.; Fickle, R. K.

    1981-01-01

    The reported observations were made with the aid of the Cosmic Ray Isotope Instrument System (CRISIS) which had been designed to detect and resolve the isotopes of cosmic ray nuclei with atomic numbers equal to or greater than 10. The CRISIS detector was flown on a balloon launched from Aberdeen, South Dakota on 1977 May 20. The period 1977 May 19-22 has been classified by Mason et al. (1979) as one of 'superquiet' solar activity, characterized by the lowest fluxes of low-energy solar particles ever observed. The obtained results are presented in a number of graphs and tables. It was found that the elemental and isotopic abundances of Si are solar-like. Elemental S is underabundant in the cosmic rays by a factor of approximately 3 relative to the solar system, but its isotopic composition resembles the solar composition with S-32 being the dominant isotope. Elemental Ar is virtually absent in the source, and the observed isotopic composition is consistent with a secondary origin. Elemental Ni has a solar-like abundance.

  1. Oxygen isotope composition of sulfate produced during microbial sulfur oxidation: A pathway-specific fingerprint?

    NASA Astrophysics Data System (ADS)

    Pjevac, P.; Brunner, B.; Mußmann, M.

    2012-04-01

    The oxidation of zero-valent sulfur such as elemental sulfur (S0) is an important energy source in many marine habitats including deep-sea vents, pelagic redox-clines and coastal surface sediments. Many microorganisms oxidize elemental sulfur to sulfate to gain reducing power. This transformation is catalyzed by a few known enzymatic pathways such as the reverse dissimilatory sulfite reductase (rDSR)-aprAB/Sor pathway or the Sox multienzyme pathway. The isotopic composition of oxygen and sulfur in produced sulfate (δ34S and δ18O) is determined by the isotope composition of the reactants, the ratio between forward and backward fluxes of enzymatically catalyzed reaction steps, and by kinetic and equilibrium isotopic fractionation. We hypothesize that the activity of distinct oxidation pathways is reflected in different δ34S and particularly, in unique δ18O isotopic fingerprints in the produced sulfate. To test our hypothesis we grew pure cultures of photo- and chemoautotrophic sulfur-oxidizing microorganisms of different phylogenetic origin with S0 as sole source of reducing power and determined the sulfur and oxygen isotope composition of the produced sulfate. The identification of characteristic isotope fingerprints for each sulfur oxidation pathway could serve as a tool to estimate and deduce the importance of certain enzymatic pathways and sulfur-oxidizing microorganisms in the environment.

  2. Measurement of natural carbon isotopic composition of acetone in human urine.

    PubMed

    Yamada, Keita; Ohishi, Kazuki; Gilbert, Alexis; Akasaka, Mai; Yoshida, Naohiro; Yoshimura, Ryoko

    2016-02-01

    The natural carbon isotopic composition of acetone in urine was measured in healthy subjects using gas chromatography-combustion-isotope ratio mass spectrometry combined with headspace solid-phase microextraction (HS-SPME-GC-C-IRMS). Before applying the technique to a urine sample, we optimized the measurement conditions of HS-SPME-GC-C-IRMS using aqueous solutions of commercial acetone reagents. The optimization enabled us to determine the carbon isotopic compositions within ±0.2 ‰ of precision and ±0.3‰ of error using 0.05 or 0.2 mL of aqueous solutions with acetone concentrations of 0.3-121 mg/L. For several days, we monitored the carbon isotopic compositions and concentrations of acetone in urine from three subjects who lived a daily life with no restrictions. We also monitored one subject for 3 days including a fasting period of 24 h. These results suggest that changes in the availability of glucose in the liver are reflected in changes in the carbon isotopic compositions of urine acetone. Results demonstrate that carbon isotopic measurement of metabolites in human biological samples at natural abundance levels has great potential as a tool for detecting metabolic changes caused by changes in physiological states and disease. Graphical abstract The natural carbon isotopic composition of acetone in urine can be determined using HS-SPME-GCC-IRMS and can provide information on changes in the availability of glucose in the liver. PMID:26718914

  3. Is my C isotope excursion global, local, or both? Insights from the Mg and Ca isotopic composition of primary, diagenetic, and authigenic carbonates

    NASA Astrophysics Data System (ADS)

    Higgins, J. A.; Blättler, C. L.; Husson, J. M.

    2014-12-01

    The C isotopic composition of ancient limestones and dolomites is a widely used proxy for the global geochemical cycles of carbon and oxygen in the ocean-atmosphere system and a critical tool for chemostratigraphy in Precambrian rocks. Although relatively robust to diagenesis, the C isotopic composition of bulk carbonates can be reset when conditions favor high water-to-rock ratios or fluids with high C concentrations and distinct isotopic compositions. Authigenic carbonates and different pools of primary carbonate (e.g. calcite vs. aragonite) may also bias the C isotopic composition of bulk carbonates if they are both abundant and isotopically distinct. New approaches to quantifying contributions from diagenesis, authigenesis, and mixing of primary carbonates to the C isotopic composition of bulk sedimentary carbonates are needed. Here we present preliminary Mg and Ca isotope data sets of primary, diagenetic, and authigenic carbonates, both modern and ancient. We show that recrystallization, dolomitization, and authigenesis produce Mg and Ca isotope fingerprints that may be used to identify and characterize these processes in ancient carbonate sediments.

  4. The anatectic effect on the zircon Hf isotope composition of migmatites and associated granites

    NASA Astrophysics Data System (ADS)

    Chen, Yi-Xiang; Gao, Peng; Zheng, Yong-Fei

    2015-12-01

    Zircon Hf isotope composition is widely used to trace the growth and evolution of continental crust. However, it is controversial whether the Hf isotope composition of magmatic zircons can faithfully reflect that of their sources, especially for S-type granites. In order to provide an insight into this issue, we have revisited the published Lu-Hf isotope data of zircons from well-studied migmatites and associated granites in the Sulu orogen and the Cathaysian terrane, respectively. The results show greatly elevated 176Hf/177Hf ratios (by more than 10ε units) for newly grown zircon domains compared to the relict zircon domains. This indicates considerable contributions from non-zircon Hf to anatectic melts during crustal anatexis and subsequent magmatism. Furthermore, this more radiogenic Hf isotope signature was not erased during magmatic processes such as crystal fractionation during melt ascent and emplacement. The budget of Hf isotopes in source rocks with respect to mineral Lu/Hf ratios suggests the involvement of Hf-bearing major minerals in anatectic reactions by dissolving Hf-bearing major minerals into the anatectic melts. The significant Hf isotope variations in some anatectic and magmatic zircon domains from the migmatites and granites suggest not only the source heterogeneity but also the variable non-zircon Hf contributions. As such, the Hf isotope compositions of anatectic and magmatic zircons are substantially dictated by the mass balance between the non-zircon Hf from anatectic reactions and the zircon-Hf from the dissolution of protolith zircons into the anatectic melts. They are primarily controlled by P-T conditions and mechanism of crustal anatexis, and the magmatic processes during melt evolution. The present study highlights the important contribution of non-zircon Hf to the anatectic and magmatic zircon domains. In this regard, the greatly elevated 176Hf/177Hf ratios for newly grown zircon domains in the migmatites and granites cannot reflect

  5. Comparing Absolute Error with Squared Error for Evaluating Empirical Models of Continuous Variables: Compositions, Implications, and Consequences

    NASA Astrophysics Data System (ADS)

    Gao, J.

    2014-12-01

    Reducing modeling error is often a major concern of empirical geophysical models. However, modeling errors can be defined in different ways: When the response variable is continuous, the most commonly used metrics are squared (SQ) and absolute (ABS) errors. For most applications, ABS error is the more natural, but SQ error is mathematically more tractable, so is often used as a substitute with little scientific justification. Existing literature has not thoroughly investigated the implications of using SQ error in place of ABS error, especially not geospatially. This study compares the two metrics through the lens of bias-variance decomposition (BVD). BVD breaks down the expected modeling error of each model evaluation point into bias (systematic error), variance (model sensitivity), and noise (observation instability). It offers a way to probe the composition of various error metrics. I analytically derived the BVD of ABS error and compared it with the well-known SQ error BVD, and found that not only the two metrics measure the characteristics of the probability distributions of modeling errors differently, but also the effects of these characteristics on the overall expected error are different. Most notably, under SQ error all bias, variance, and noise increase expected error, while under ABS error certain parts of the error components reduce expected error. Since manipulating these subtractive terms is a legitimate way to reduce expected modeling error, SQ error can never capture the complete story embedded in ABS error. I then empirically compared the two metrics with a supervised remote sensing model for mapping surface imperviousness. Pair-wise spatially-explicit comparison for each error component showed that SQ error overstates all error components in comparison to ABS error, especially variance-related terms. Hence, substituting ABS error with SQ error makes model performance appear worse than it actually is, and the analyst would more likely accept a

  6. The multiple sulfur isotopic composition of iron meteorites: Implications for nebular evolution

    NASA Astrophysics Data System (ADS)

    Antonelli, Michael Ariel

    2013-12-01

    Multiple sulfur isotopic measurements of troilite from 61 different iron meteorites were undertaken in order to test for sulfur isotopic homogeneity within (and between) 8 different iron meteorite groups. It was found that different members within a given group of iron meteorites have homogeneous Delta 33S compositions, but that these Delta33S compositions differ between groups. This thesis shows that iron meteorites from the groups IC, IIAB, IIIAB, IIIF, and IVA have small yet resolvable enrichments or depletions in Delta33S relative to Canyon Diablo Troilite (CDT) and troilite from other non-magmatic (IAB and IIE) iron meteorites. The observed anomalous sulfur isotopic compositions in magmatic iron meteorites are most consistent with Lyman-alpha photolysis of H2S, pointing towards inheritance of an unexpected photolytically-derived sulfur component in magmatic iron meteorite groups which is absent in non-magmatic iron meteorites, chondrites, and the Earth-Moon System.

  7. The oxygen isotopic composition of the Sun inferred from captured solar wind.

    PubMed

    McKeegan, K D; Kallio, A P A; Heber, V S; Jarzebinski, G; Mao, P H; Coath, C D; Kunihiro, T; Wiens, R C; Nordholt, J E; Moses, R W; Reisenfeld, D B; Jurewicz, A J G; Burnett, D S

    2011-06-24

    All planetary materials sampled thus far vary in their relative abundance of the major isotope of oxygen, (16)O, such that it has not been possible to define a primordial solar system composition. We measured the oxygen isotopic composition of solar wind captured and returned to Earth by NASA's Genesis mission. Our results demonstrate that the Sun is highly enriched in (16)O relative to the Earth, Moon, Mars, and bulk meteorites. Because the solar photosphere preserves the average isotopic composition of the solar system for elements heavier than lithium, we conclude that essentially all rocky materials in the inner solar system were enriched in (17)O and (18)O, relative to (16)O, by ~7%, probably via non-mass-dependent chemistry before accretion of the first planetesimals. PMID:21700868

  8. Isotopic and Elemental Composition of Roasted Coffee as a Guide to Authenticity and Origin.

    PubMed

    Carter, James F; Yates, Hans S A; Tinggi, Ujang

    2015-06-24

    This study presents the stable isotopic and elemental compositions of single-origin, roasted coffees available to retail consumers. The δ(13)C, δ(15)N, and δ(18)O compositions were in agreement with those previously reported for green coffee beans. The δ(15)N composition was seen to be related to organic cultivation, reflected in both δ(2)H and δ(18)O compositions. The δ(13)C composition of extracted caffeine differed little from that of the bulk coffee. Stepwise discriminant analysis with jackknife tests, using isotopic and elemental data, provided up to 77% correct classification of regions of production. Samples from Africa and India were readily classified. The wide range in both isotopic and elemental compositions of samples from other regions, specifically Central/South America, resulted in poor discrimination between or within these regions. Simpler X-Y and geo-spatial plots of the isotopic data provided effective visual means to distinguish between coffees from different regions. PMID:26001050

  9. High Temporal Resolution Measurements and Modeling of the Isotopic Composition of Methane in Europe

    NASA Astrophysics Data System (ADS)

    Popa, E.; Röckmann, T.; Eyer, S.; van der Veen, C.; Tuzson, B.; Monteil, G.; Houweling, S.; Harris, E. J.; Brunner, D.; Fischer, H.; Fisher, R. E.; Lowry, D.; Nisbet, E. G.; Emmenegger, L.; Mohn, J.

    2015-12-01

    Isotope measurements can help constraining the atmospheric budget of methane because different sources emit methane with slightly different isotopic composition. In the past, high precision isotope measurements have primarily been carried out by isotope ratio mass spectrometry on flask samples that are usually collected at relatively low temporal resolution. During the EU project INGOS, we have deployed a fully automated gas chromatography - isotope ratio mass spectrometry system (GC-IRMS), together with two laser instruments, during a 4-months campaign in the field at the Cabauw Experimental Site for Atmospheric Research (CESAR). More than 1600 measurements for δ13C and δD were obtained with IRMS during this period. Measurements show clear isotope signals associated with methane elevations both on the diurnal as well as the synoptic scale. In order to assess the added value of such measurements for constraining the CH4 budget, we performed coupled simulations of CH4 and δ13C-CH4 using the chemistry transport model TM5. We specifically assessed the relative impact of uncertainties in i) CH4 emissions, ii) CH4 isotope source signatures and iii) methane transport and chemistry throughout the atmosphere. By randomly perturbing CH4 emissions and δ13C source signatures, we identified areas where simulated variations are dominated by uncertainties in the emission strength and areas where uncertainties in the isotope signatures dominate. At observation sites where the uncertainties in CH4 emissions dominate the other sources of uncertainty, isotope observations should provide useful additional constraints on CH4 emissions. At locations where uncertainties in the isotope signatures dominate, the isotope measurements will be useful to better constrain the source signatures themselves.

  10. Isotopic composition of trace elements in presolar silicon carbide A+B grains

    NASA Astrophysics Data System (ADS)

    Savina, M.; Tripa, C.; Pellin, M.; Davis, A.; Clayton, R.; Lewis, R.; Amari, S.

    2003-04-01

    Presolar SiC are classified into several types based on C, N, and Si isotopic compositions. Most are mainstream, which are generally believed to derive from low-mass asymptotic giant branch (AGB) stars. Among the less common grains, A+B grains, which comprise ˜3-4% of presolar SiC, are perhaps the least well understood. Recent measurements of trace element concentration patterns in individual grains suggest that A+B grains can be divided into at least 4 groups, and thus have multiple astrophysical sites of origin^1. We report here our Resonant Ionization Mass Spectrometry (RIMS) measurements of Zr, Mo, Ba, and Fe isotopic compositions in individual mainstream and type A+B presolar SiC. While the mainstream grains show isotopic compositions compatible with condensation around low-mass AGB stars, most A+B grains have near-solar isotopic compositions, though some show Zr, Mo, and Fe isotope patterns that have not been observed in other types of presolar SiC grains. We discuss these results in terms of possible astrophysical sites for the production of these unusual grains. This work was supported in part by the Department of Energy, BES-Materials Sciences through Contract No. W-31-109-ENG-38. ^1 Amari S., Nittler L. R., Zinner E., Lodders K., and Lewis R. S. (2001) Astrophys. J. 559, 463-483.

  11. Oxygen and Sulfur Isotope Composition of Dissolved Sulfate in Interstitial Waters of the Great Australian Bight, ODP Leg 182.

    NASA Astrophysics Data System (ADS)

    Bernasconi, S. M.; Böttcher, M. E.; Wormann, U. G.

    2005-12-01

    We measured the sulfur and oxygen isotope composition of dissolved sulfides and sulfate at ODP Sites 1129, 1130, 1131 and 1132 in the Great Australian Bight (GAB). At all Sites, a saline brine is present in the subsurface as indicated by increasing chloride concentrations with depth to reach contents up to 3 times seawater. Sulfate also increases with depth but the concentrations are reduced by intense microbial sulfate reduction. The sulfur isotope fractionation between coexisting dissolved sulfate and sulfide is very large and reaches up to 70 ‰ at all studied Sites. Due to the high sulfide concentrations and the lack of a significant source of oxidants we consider that the large sulfur isotope fractionations are induced by sulfate reducing bacteria alone without a significant contribution of elemental sulfur disproportionation and sulfide oxidation processes. The oxygen isotope composition of dissolved sulfate reaches maximum values of approximately +27 ‰ vs. VSMOW at all sites, close to the equilibrium isotope fractionation between sulfate and water. The oxygen isotope composition of dissolved sulfate positively correlates with the sulfur isotope fractionation between sulfate and sulfide. These oxygen isotope data thus support the hypothesis that that the high sulfur isotope fractionation are related to a single step fractionation by sulfate reducing bacteria and do not involve significant sulfide oxidation reactions and/or elemental sulfur disproportionation. Sulfide oxidation processes would lead to a lowering of the oxygen isotope composition of residual sulfate. Elemental sulfur disproportionation has been shown to increase the oxygen isotope composition of sulfate but to a smaller extent than that that observed in the GAB. The patterns of the oxygen isotope increase with progressive sulfate reduction indicate a predominant influence of isotope exchange rather than a kinetic isotope fractionation controlling the oxygen isotope composition of sulfate

  12. Vanadium isotopic composition of the sea squirt (Ciona savignyi).

    PubMed

    Nomura, Masao; Nakamura, Mana; Soeda, Ryosuke; Kikawada, Yoshikazu; Fukushima, Michiko; Oi, Takao

    2012-09-01

    Vanadium (V) in the sea squirt (Ciona savignyi) from Onagawa Bay, Miyagi, Japan, was isolated and purified through adsorption on a diamine resin and anion and cation exchanges after the dissolution of sea squirt samples with nitric acid and hydrogen peroxide. The (50)V/(51)V isotope ratio of V thus obtained was mass-spectrometrically determined to be from 2.51×10(-3) to 2.55×10(-3) with the average of 2.53×10(-3) by the thermal ionisation technique. This value agreed with those of vanadyl chloride and vanadyl nitrate both prepared from vanadyl sulphate (Wako Pure Chemical Industries, Ltd., Japan) and of V in coastal seawater (Shimokita Peninsula, Aomori, Japan) within experimental uncertainties (standard deviation of±0.04), which suggested that no appreciable V isotope fractionation occurs accompanying V uptake by the sea squirt from sea water. PMID:22462478

  13. [Carbon Isotope Composition in Landscape Components and Its Changes under Different Ecological Conditions].

    PubMed

    Kovda, I V; Morgun, E G; Gongalskii, K B; Balandin, S A; Erokhina, A I

    2016-01-01

    The composition of stable carbon isotopes in plants, plant litter, leaf litter, and soil organic matter was studied experimentally in the western part of the northern foothills of the Caucasus and mountainsides. It was found that the changes in carbon isotope composition depending on the vertical zonation do not exceed 8 per thousand and depend on the type of C3 plant communities, its presence in biogeocenosis components (living matter, plant litter, soil organic matter), and the degree of moistening of the plot studied. PMID:27396183

  14. Composition dependence of the interaction parameter in isotopic polymer blends

    SciTech Connect

    Londono, J.D.; Narten, A.H.; Wignall, G.D. ); Honnell, K.G.; Hsieh, E.T.; Johnson, T.W. . Research and Development); Bates, F.S. . Dept. of Chemical Engineering)

    1994-05-09

    Isotopic polymer mixtures lack the structural asymmetries and specific interactions encountered in blends of chemically distinct species. In this respect, they form ideal model systems for exploring the limitations of the widely-used Flory-Huggins (FH) lattice model and for testing and improving new theories of polymer thermodynamics. The FH interaction parameter between deuterium-labeled and unlabeled segments of the same species ([sub [chi]HD]) should in principle be independent of concentration ([phi]), through previous small-angle neutron scattering (SANS) experiments have shown that it exhibits a minimum at [phi] [approximately] 0.5 for poly(vinylethylene) (PVE) and poly(ethylethylene) (PEE). The authors report new data on polyethylene (PE) as a function of molecular weight, temperature (T), and [phi], which show qualitatively similar behavior. However, measurements on [sub [chi]HD]([phi]) for polystyrene (PS) show a maximum at [phi] [approximately]0.5, in contrast to PVE, PEE, and PE. Reproducing the concentration dependence of [phi] in different model isotopic systems should serve as a sensitive test of the way in which theories of polymer thermodynamics can account for the details of the local packing and also the effects of noncombinatorial entropy, which appear to be the main cause of the variation of [sub [chi]HD]([phi]) for PE. These data also serve to quantify the effects of isotopic substitution in SANS experiments on polyolefin blends and thus lay the ground work for definitive studies of the compatibility of branched and linear polyethylenes.

  15. Long-term monitoring of stable isotopic compositions of precipitation over volcanic island, Jeju, Korea

    NASA Astrophysics Data System (ADS)

    Kim, Young-Hee; Koh, Dong-Chan; Park, Won-Bae; Bong, Yeon-Sik; Lee, Kwang-Sik; Lee, Jeonghoon

    2015-04-01

    Stable isotopic compositions of precipitation can be widely used to understand moisture transport in the atmosphere, proxies for paleoclimate and interactions between groundwater and precipitation. Over Jeju volcanic island, located southwest of the Korean Peninsula, precipitation penetrated directly into the highly permeable aquifer is the main source of groundwater. In this study, long-term stable isotopic compositions of precipitation over Jeju Island are characterized to describe spatial and temporal patterns for hydrology and paleoclimate. At fifteen sites from September 2000 to December 2003, precipitation samples were collected and analyzed by Isotope Ratio Mass Spectrometer at the Korea Basic Science Institute. Compared to Lee et al. (2003), the two seasonal local meteoric water lines widen, which may change the relative contributions of winter and summer season precipitation to the groundwater recharge. The precipitation isotopes are inversely correlated with precipitation amount in summer, whereas they do not show a strong correlation with surface air temperature. The precipitation isotopes monthly averaged relatively show a periodic function (R2=0.63 and 0.40 for hydrogen and oxygen, respectively), and deuterium excess (d-excess=δD-8×δ18O) shows a strong pattern of quadratic function (R2=0.97), which is related to a seasonal change of air masses. Altitude effect of precipitation isotopes, which can be a clue to reveal sources of groundwater, can be observed in every aspect of the volcanic island (for the oxygen isotope, -0.14‰ for east and west, -0.18‰ for north and -0.085‰ for south per 100 m). Our analysis of precipitation isotopes will be helpful to provide limitations and opportunities for paleoclimate reconstruction using isotopic proxies and water movement from atmosphere to subsurface.

  16. Absolute frequency and isotope shift of the magnesium (3 s2) 1S0→(3 s 3 d ) 1D2 two-photon transition by direct frequency-comb spectroscopy

    NASA Astrophysics Data System (ADS)

    Peters, E.; Reinhardt, S.; Hänsch, Th. W.; Udem, Th.

    2015-12-01

    We use a picosecond frequency-doubled mode-locked titanium sapphire laser to generate a frequency comb at 431 nm in order to probe the (3 s2) 1S0 →(3 s 3 d ) 1D2 transition in atomic magnesium. Using a second, self-referenced femtosecond frequency comb, the absolute transition frequency and the 24Mg and 26Mg isotope shift is determined relative to a global-positioning-system-referenced hydrogen maser. Our result for the transition frequency of the main isotope 24Mg of 1 391 128 606.14 (12 ) MHz agrees with previous measurements and reduces its uncertainty by four orders of magnitude. For the isotope shift we find δ ν26 ,24=3915.13 (39 ) MHz. Accurate values for transition frequencies in Mg are relevant in astrophysics and to test atomic structure calculations.

  17. Anomalous sulfur isotope compositions of volcanic sulfate over the last millennium in Antarctic ice cores

    NASA Astrophysics Data System (ADS)

    Baroni, MéLanie; Savarino, JoëL.; Cole-Dai, Jihong; Rai, Vinai K.; Thiemens, Mark H.

    2008-10-01

    The reconstruction of past volcanism from glaciological archives is based on the measurement of sulfate concentrations in ice. This method does not allow a proper evaluation of the climatic impact of an eruption owing to the uncertainty in classifying an event between stratospheric or tropospheric. This work develops a new method, using anomalous sulfur isotope composition of volcanic sulfate in order to identify stratospheric eruptions over the last millennium. The advantages and limits of this new method are established with the examination of the 10 largest volcanic signals in ice cores from Dome C and South Pole, Antarctica. Of the 10, seven are identified as stratospheric eruptions. Among them, three have been known to be stratospheric (Tambora, Kuwae, the 1259 Unknown Event) and they exhibit anomalous sulfur isotope compositions. Three unknown events (circa 1277, 1230, 1170 A.D.) and the Serua eruption have been identified as stratospheric eruptions, which suggests for the first time that they could have had significant climatic impact. However, the Kuwae and the 1259 Unknown Event stratospheric eruptions exhibit different anomalous sulfur isotope compositions between South Pole and Dome C samples. Differences in sulfate deposition and preservation patterns between the two sites can help explain these discrepancies. This study shows that the presence of an anomalous sulfur isotope composition of volcanic sulfate in ice core indicates a stratospheric eruption, but the absence of such composition does not necessarily lead to the conclusion of a tropospheric process because of differences in the sulfate deposition on the ice sheet.

  18. Molybdenum Isotopic Composition of the Archean Mantle As Inferred from Studies of Komatiites

    NASA Astrophysics Data System (ADS)

    Greber, N. D.; Puchtel, I. S.; Nagler, T. F.; Mezger, K.

    2014-12-01

    Molybdenum isotopic composition has been shown to be a powerful tool in studies of planetary processes, e.g. estimating core formation temperatures [1,2]. However, Mo isotope compositions of terrestrial reservoirs are not well constrained. In order to better constrain the Mo isotopic composition of the early Earth's mantle, komatiites from four locations were analyzed for their Mo concentrations and isotopic compositions. Komatiites are particularly appropriate for this type of study because they formed by high degrees of partial melting of the mantle leading to a complete base metal sulfide removal from the residual mantle and the production of sulfur-undersaturated melts and thus a quantitative removal of Mo from the source into the melt. All samples, except for two strongly altered specimens specifically chosen to study the effects of secondary alteration, are very fresh having preserved most of their primary mineralogy. The Mo concentrations in komatiites range from 10 to 120 ng/g. Fresh komatiites have lighter δ98Mo (NIST SRM 3134 = 0.25‰, [3]) than altered samples. The estimated primary Mo isotope compositions of the studied komatiite melts range from 0.02 ± 0.16‰ to 0.19 ± 0.14‰ and are therefore indistinguishable within analytical uncertainty (2SD) from published values for chondritic meteorites (0.09 ± 0.04 ‰; 2SD; [2]) and lighter than the proposed average for Earth's continental crust (0.3 to 0.4‰ [4]). All data combined, although overlapping in errors, show a consistent trend of lighter δ98Mo and lower Mo concentrations in more melt-depleted mantle sources, indicating incompatible behaviour of Mo and preferential mobilization of heavy Mo isotopes during mantle melting. [1] Hin et al. (2013) EPSL, 379 [2] Burkhardt et al. (2014) EPSL, 391 [3] Nägler, et al. (2014) GGR, 38. [4] Voegelin et al. (2014) Lithos, 190-191.

  19. Moisture sources of precipitation over Postojna (Slovenia) and implication of its oxygen isotope composition

    NASA Astrophysics Data System (ADS)

    Krklec, Kristina; Domínguez-Villar, David; Lojen, Sonja

    2016-04-01

    The source of moisture is an important part of the hydrological cycle that affects climate system. Potentially, moisture sources are important controls of the isotope composition of precipitation, but their studies in the continental mid- and low-latitudes are still scarce due to the complexity of general circulation models with integrated isotope modules. We identify moisture uptake locations of precipitation over Postojna (Slovenia) for period from 2009 to 2013. By using HYSPLIT trajectory model of NOAA we did 5-day reconstruction of air mass history for the days with precipitation and determination of moisture uptake locations along back trajectories. Moisture uptake locations were identified along each trajectory using HYSPLIT output data and standard equations for saturation humidity mixing ratio, saturation vapour pressure and specific humidity. Although NNE winds were prevailing during the period 2001-2014, our analysis showed that during this period around 45% of the precipitation over Postojna originated from Mediterranean and south Atlantic area, with majority of locations originated in the Adriatic Sea. On the other hand, 41% of precipitation originated from moisture recycled over continents, predominantly from Pannonian basin. The comparison of monthly oxygen isotope composition of precipitation with the percentage of precipitation originated in different source regions shows a significant correlation only for the north Atlantic region. However, less than 7% of the variability of oxygen isotope composition of precipitation is associated with this moisture source. Multivariable analyses of source regions do not explain any additional variability of the oxygen isotope composition of precipitation over Postojna. This research shows that at this location, although significant, moisture sources are not important controls of the oxygen isotope composition of precipitation.

  20. The effect of phosphomonoesterases on the oxygen isotope composition of phosphate

    NASA Astrophysics Data System (ADS)

    von Sperber, Christian; Kries, Hajo; Tamburini, Federica; Bernasconi, Stefano M.; Frossard, Emmanuel

    2014-01-01

    Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. During the enzymatic hydrolysis an isotopic fractionation (ε) occurs leaving an imprint on the oxygen isotope composition of the released Pi which might be used to trace phosphorus in the environment. Therefore, enzymatic assays with acid phosphatases from wheat germ and potato tuber and alkaline phosphatase from Escherichia coli were prepared in order to determine the oxygen isotope fractionation caused by these enzymes. Adenosine 5‧ monophosphate and glycerol phosphate were used as substrates. The oxygen isotope fractionation caused by acid phosphatases is 20-30‰ smaller than for alkaline phosphatases, resulting in a difference of 5-7.5‰ in δ18O of Pi depending on the enzyme. We attribute the enzyme dependence of the isotopic fractionation to distinct reaction mechanisms of the two types of phosphatases. The observed difference is large enough to distinguish between the two enzymatic processes in environmental samples. These findings show that the oxygen isotope composition of Pi can be used to trace different enzymatic processes, offering an analytical tool that might contribute to a better understanding of the P-cycle in the environment.

  1. H, C, and N isotopic compositions of Hayabusa category 3 organic samples

    NASA Astrophysics Data System (ADS)

    Ito, Motoo; Uesugi, Masayuki; Naraoka, Hiroshi; Yabuta, Hikaru; Kitajima, Fumio; Mita, Hajime; Takano, Yoshinori; Karouji, Yuzuru; Yada, Toru; Ishibashi, Yukihiro; Okada, Tatsuaki; Abe, Masanao

    2014-08-01

    Since isotopic ratios of H, C, and N are sensitive indicators for determining extraterrestrial organics, we have measured these isotopes of Hayabusa category 3 organic samples of RB-QD04-0047-02, RA-QD02-0120, and RB-QD04-0001 with ion imaging using a NanoSIMS ion microprobe. All samples have H, C, and N isotopic compositions that are terrestrial within errors (approximately ±50‰ for H, approximately ±9‰ for C, and approximately ±2‰ for N). None of these samples contain micrometer-sized hot spots with anomalous H, C, and N isotopic compositions, unlike previous isotope data for extraterrestrial organic materials, i.e., insoluble organic matters (IOMs) and nano-globules in chondrites, interplanetary dust particles (IDPs), and cometary dust particles. We, therefore, cannot conclude whether these Hayabusa category 3 samples are terrestrial contaminants or extraterrestrial materials because of the H, C, and N isotopic data. A coordinated study using microanalysis techniques including Fourier transform infrared spectrometry (FT-IR), time-of-flight secondary ion mass spectrometry (ToF-SIMS), NanoSIMS ion microprobe, Raman spectroscopy, X-ray absorption near edge spectroscopy (XANES), and transmission electron microscopy/scanning transmission electron microscopy (TEM/STEM) is required to characterize Hayabusa category 3 samples in more detail for exploring their origin and nature.

  2. Plutonium isotopes in the atmosphere of Central Europe: Isotopic composition and time evolution vs. circulation factors.

    PubMed

    Kierepko, Renata; Mietelski, Jerzy W; Ustrnul, Zbigniew; Anczkiewicz, Robert; Wershofen, Herbert; Holgye, Zoltan; Kapała, Jacek; Isajenko, Krzysztof

    2016-11-01

    This paper reports evidence of Pu isotopes in the lower part of the troposphere of Central Europe. The data were obtained based on atmospheric aerosol fraction samples collected from four places in three countries (participating in the informal European network known as the Ring of Five (Ro5)) forming a cell with a surface area of about 200,000km(2). We compared our original data sets from Krakow (Poland, 1990-2007) and Bialystok (Poland, 1991-2007) with the results from two other locations, Prague (Czech Republic; 1997-2004) and Braunschweig (Germany; 1990-2003) to find time evolution of the Pu isotopes. The levels of the activity concentration for (238)Pu and for ((239+240))Pu were estimated to be a few and some tens of nBqm(-3), respectively. However, we also noted some results were much higher (even about 70 times higher) than the average concentration of (238)Pu in the atmosphere. The achieved complex data sets were used to test a new approach to the problem of solving mixing isotopic traces from various sources (here up to three) in one sample. Results of our model, supported by mesoscale atmospheric circulation parameters, suggest that Pu from nuclear weapon accidents or tests and nuclear burnt-up fuel are present in the air. PMID:27450248

  3. Carbon isotope composition of latex does not reflect temporal variations of photosynthetic carbon isotope discrimination in rubber trees (Hevea brasiliensis).

    PubMed

    Kanpanon, Nicha; Kasemsap, Poonpipope; Thaler, Philippe; Kositsup, Boonthida; Gay, Frédéric; Lacote, Régis; Epron, Daniel

    2015-11-01

    Latex, the cytoplasm of laticiferous cells localized in the inner bark of rubber trees (Hevea brasiliensis Müll. Arg.), is collected by tapping the bark. Following tapping, latex flows out of the trunk and is regenerated, whereas in untapped trees, there is no natural exudation. It is still unknown whether the carbohydrates used for latex regeneration in tapped trees is coming from recent photosynthates or from stored carbohydrates, and in the former case, it is expected that latex carbon isotope composition of tapped trees will vary seasonally, whereas latex isotope composition of untapped trees will be more stable. Temporal variations of carbon isotope composition of trunk latex (δ(13)C-L), leaf soluble compounds (δ(13)C-S) and bulk leaf material (δ(13)C-B) collected from tapped and untapped 20-year-old trees were compared. A marked difference in δ(13)C-L was observed between tapped and untapped trees whatever the season. Trunk latex from tapped trees was more depleted (1.6‰ on average) with more variable δ(13)C values than those of untapped trees. δ(13)C-L was higher and more stable across seasons than δ(13)C-S and δ(13)C-B, with a maximum seasonal difference of 0.7‰ for tapped trees and 0.3‰ for untapped trees. δ(13)C-B was lower in tapped than in untapped trees, increasing from August (middle of the rainy season) to April (end of the dry season). Differences in δ(13)C-L and δ(13)C-B between tapped and untapped trees indicated that tapping affects the metabolism of both laticiferous cells and leaves. The lack of correlation between δ(13)C-L and δ(13)C-S suggests that recent photosynthates are mixed in the large pool of stored carbohydrates that are involved in latex regeneration after tapping. PMID:26358051

  4. Determining terrestrial paleotemperatures using the oxygen isotopic composition of pedogenic carbonate

    NASA Astrophysics Data System (ADS)

    Dworkin, S. I.; Nordt, L.; Atchley, S.

    2005-08-01

    Quantifying terrestrial paleotemperatures has proven to be a challenging endeavor. This paper explores the use of the oxygen isotopic composition of pedogenic calcite for terrestrial paleotemperature reconstructions. We generate three paleotemperature equations, two of them derived by simultaneous solution of equations that describe the fractionation of oxygen isotopes in the exogenic cycle, while the third equation is derived using a linear regression through modern δ18Occ / MAT (oxygen isotopic composition of pedogenic calcite versus mean annual temperature) data. We use the paleotemperature equations to evaluate climate change across the K-T boundary by analyzing the oxygen isotopic composition of pedogenic carbonates from a series of stacked paleosols in west Texas. The fabrics in the calcite nodules were evaluated in order to identify soil carbonate components that have the best chance of containing isotopic information that represents ancient pedogenic conditions. The average temperature for West Texas during the time period studied is 18+ / - 0.5 °C. Two temperature excursions are recognized prior to the K-T boundary in which terrestrial temperatures increase by about 4 °C for relatively short periods of time. These short greenhouse events documented in west Texas correlate with changes in marine temperatures as well as terrestrial temperatures in North Dakota during the same time period. Latitudinal temperature gradients generated using the West Texas and North Dakota data indicate that the spatial simultaneous solution yields the most reliable temperature reconstructions of the three equations considered in this study.

  5. Oxygen and carbon isotopic compositions of gases respired by humans

    SciTech Connect

    Epstein, S.; Zeiri, L. )

    1988-03-01

    Oxygen-isotope fractionation associated with respiration in human individuals at rest is linearly related to the fraction of the O{sub 2} utilized in the respiration process. The slope of this relationship is affected by a history of smoking, by vigorous exercise, and by the N{sub 2}/O{sub 2} ratio of the inhaled gas. For patients who suffer anemia-related diseases, the slope of this relationship is directly proportional to their level of hemoglobin. These results introduce a new approach for studying the mechanisms of O{sub 2} consumption in human respiration and how they are affected by related diseases.

  6. Satellite measurements of the isotopic composition of galactic cosmic rays

    NASA Technical Reports Server (NTRS)

    Mewaldt, R. A.; Spalding, J. D.; Stone, E. C.; Vogt, R. E.

    1979-01-01

    The individual isotopes of galactic cosmic ray Ne, Mg, and Si at 100 MeV/nucleon were clearly resolved with an rms mass resolution of 0.20 amu. The results suggest the cosmic ray source is enriched in Ne-22, Mg-25, and Mg-26 when compared to the solar system. The ratio of (Mg-25)+(Mg-26) to Mg-24, which is approximately 0.49 compared to the solar system value of 0.27, suggest that the cosmic ray source and solar system material were synthesized under different conditions.

  7. Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide

    PubMed Central

    Wiegel, Aaron A.; Cole, Amanda S.; Hoag, Katherine J.; Atlas, Elliot L.; Schauffler, Sue M.; Boering, Kristie A.

    2013-01-01

    We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in 17O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone–CO2 isotope exchange demonstrates that non–mass-dependent isotope effects in ozone formation alone quantitatively account for the 17O anomaly in CO2 in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O3, O(1D), or CO2 and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of 17O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2. PMID:23940331

  8. Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide.

    PubMed

    Wiegel, Aaron A; Cole, Amanda S; Hoag, Katherine J; Atlas, Elliot L; Schauffler, Sue M; Boering, Kristie A

    2013-10-29

    We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in (17)O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone-CO2 isotope exchange demonstrates that non-mass-dependent isotope effects in ozone formation alone quantitatively account for the (17)O anomaly in CO2 in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O3, O((1)D), or CO2 and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of (17)O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2. PMID:23940331

  9. Stable sulfur and nitrogen isotopic compositions of crude oil fractions from Southern Germany

    NASA Astrophysics Data System (ADS)

    Hirner, A. V.; Graf, W.; Treibs, R.; Melzer, A. N.; Hahn-Weinheimer, P.

    1984-11-01

    Eleven samples of crude oil from the Molasse Basin of Southern Germany were fractionated and their contents of sulfur and nitrogen as well as the stable isotope compositions of these elements ( 34S /32S and 15N /14N , resp.) investigated. According to the δ34S determinations, all crude oils from the Tertiary base of the Western and Eastern Molasse belong to one oil family and differ significantly from the Triassic and Liassic oils in the Western Molasse. An enrichment of 34S was observed with increasing polarity of crude oil fractions. The isotope distributions of sulfur in the polar constituents of the biodegraded oils from the sandstones of Ampfing, however, approach a homogeneous distribution. The nitrogen isotope distribution is rather uniform in Southern German oils. A regional differentiation can be recognized, although the overall isotopic variation is small. The δ15N values of the crudes and asphaltenes do not correlate.

  10. Isotope composition of sulphate in acid mine drainage as measure of bacterial oxidation

    USGS Publications Warehouse

    Taylor, B.E.; Wheeler, M.C.; Nordstrom, D.K.

    1984-01-01

    The formation of acid waters by oxidation of pyrite-bearing ore deposits, mine tailing piles, and coal measures is a complex biogeochemical process and is a serious environmental problem. We have studied the oxygen and sulphur isotope geochemistry of sulphides, sulphur, sulphate and water in the field and in experiments to identify sources of oxygen and reaction mechanisms of sulphate formation. Here we report that the oxygen isotope composition of sulphate in acid mine drainage shows a large variation due to differing proportions of atmospheric- and water-derived oxygen from both chemical and bacterially-mediated oxidation. 18O-enrichment of sulphate results from pyrite oxidation facilitated by Thiobacillus ferrooxidans in aerated environments. Oxygen isotope analysis may therefore be useful in monitoring the effectiveness of abatement programmes designed to inhibit bacterial oxidation. Sulphur isotopes show no significant fractionation between pyrite and sulphate, indicating the quantitative insignificance of intermediate oxidation states of sulphur under acid conditions. ?? 1984 Nature Publishing Group.

  11. First Measurements of Osmium Concentration and Isotopic Composition in a Summit, Greenland Ice Core

    NASA Astrophysics Data System (ADS)

    Osterberg, E. C.; Sharma, M.; Hawley, R. L.; Courville, Z.

    2010-12-01

    Osmium (Os) is one of the rarer elements in the environment and therefore one of the most difficult to accurately measure, but its isotopically distinctive crustal, mantle-derived, and extra-terrestrial sources make it a valuable geochemical tracer. Recent state-of-the-art analyses of precipitation, river water, and ocean water samples from around the world have revealed elevated concentrations of Os with a characteristically low (unradiogenic) Os isotopic signature (187Os/188Os). This unusual low Os isotopic signal has been interpreted as evidence for widespread Os pollution due to the smelting of Platinum Group Element (PGE) sulfide ores for use in automobile catalytic converters. However, an environmental time series of Os concentrations and isotopic composition spanning the pre-industrial to modern era has not previously been developed to evaluate changes in atmospheric Os sources through time. Here we present the first measurements of Os concentration and isotopic composition (to our knowledge) in a 100 m-long ice core collected from Summit, Greenland, spanning from ca. 1700 to 2010 AD. Due to the extremely low Os concentrations in snow (10-15 g/g), these analyses have only recently become possible with advances in Thermal Ionization Mass Spectrometry (TIMS) and ultra-clean analytical procedures. Initial results indicate that the 187Os/188Os of Greenland snow was unradiogenic (187Os/188Os = 0.13-0.15) for at least several periods over the past 300 years, including both pre-anthropogenic and modern times. Os concentrations in the Summit ice core are relatively high (11-52 pg/kg) compared to previously measured precipitation in North America, Europe, Asia and Antarctic sea ice (0.35-23 pg/kg). The low (unradiogenic) isotopic composition are consistent with extraterrestrial (cosmic dust and meteorites; 187Os/188Os = 0.13) and possibly volcanic (187Os/188Os = 0.15-0.6) Os sources, although the Os isotopic composition of volcanic emissions is poorly constrained

  12. Isotopic composition of Murchison organic compounds: Intramolecular carbon isotope fractionation of acetic acid. Simulation studies of cosmochemical organic syntheses

    NASA Technical Reports Server (NTRS)

    Yuen, G. U.; Cronin, J. R.; Blair, N. E.; Desmarais, D. J.; Chang, S.

    1991-01-01

    Recently, in our laboratories, samples of Murchison acetic acid were decarboxylated successfully and the carbon isotopic composition was measured for the methane released by this procedure. These analyses showed significant differences in C-13/C-12 ratios for the methyl and carboxyl carbons of the acetic acid molecule, strongly suggesting that more than one carbon source may be involved in the synthesis of the Murchison organic compounds. On the basis of this finding, laboratory model systems simulating cosmochemical synthesis are being studied, especially those processes capable of involving two or more starting carbon sources.

  13. Lithium contents and isotopic compositions of ferromanganese deposits from the global ocean

    USGS Publications Warehouse

    Chan, L.-H.; Hein, J.R.

    2007-01-01

    To test the feasibility of using lithium isotopes in marine ferromanganese deposits as an indicator of paleoceanographic conditions and seawater composition, we analyzed samples from a variety of tectonic environments in the global ocean. Hydrogenetic, hydrothermal, mixed hydrogenetic–hydrothermal, and hydrogenetic–diagenetic samples were subjected to a two-step leaching and dissolution procedure to extract first the loosely bound Li and then the more tightly bound Li in the Mn oxide and Fe oxyhydroxide. Total leachable Li contents vary from 2 by coulombic force. Hence, the abundant Li in hydrothermal deposits is mainly associated with the dominant phase, MnO2. The surface of amorphous FeOOH holds a slightly positive charge and attracts little Li, as demonstrated by data for hydrothermal Fe oxyhydroxide. Loosely sorbed Li in both hydrogenetic crusts and hydrothermal deposits exhibit Li isotopic compositions that resemble that of modern seawater. We infer that the hydrothermally derived Li scavenged onto the surface of MnO2 freely exchanged with ambient seawater, thereby losing its original isotopic signature. Li in the tightly bound sites is always isotopically lighter than that in the loosely bound fraction, suggesting that the isotopic fractionation occurred during formation of chemical bonds in the oxide and oxyhydroxide structures. Sr isotopes also show evidence of re-equilibration with seawater after deposition. Because of their mobility, Li and Sr in the ferromanganese crusts do not faithfully record secular variations in the isotopic compositions of seawater. However, Li content can be a useful proxy for the hydrothermal history of ocean basins. Based on the Li concentrations of the globally distributed hydrogenetic and hydrothermal samples, we estimate a scavenging flux of Li that is insignificant compared to the hydrothermal flux and river input to the ocean.

  14. Variation of lithium isotope composition in the marine environment: A preliminary report

    SciTech Connect

    Chan, Luiheung; Edmond, J.M. )

    1988-06-01

    The Li isotopic compositions of ocean waters, lake water, hydrothermal solutions, altered and unaltered basalts have been determined using the technique of thermal ionization mass spectrometry of lithium tetraborate. Seawater appears to be homogeneous in Li isotopic composition. The mean {delta}{sup 6}Li value is {minus}32.3 {plus minus} 0.5{per thousand}, relative to an isotopic standard. Three lakes studied (Lake Tanganyika, Caspian Sea and Dead Sea) yield {delta}{sup 6}Li similar to the seawater isotopic composition. A fresh basalt glass from 21{degree}N, East Pacific Rise displays a {delta}{sup 6}Li value of {minus}4.7{per thousand}. A hydrothermal solution from a 21{degree}N vent field has {delta}{sup 6}Li of {minus}10{per thousand}, indicating incomplete extraction of Li from the igneous minerals or partial retention in secondary phases. The alteration margin of a basalt from the Mid-Atlantic Ridge has {delta}{sup 6}Li of {minus}8.4{per thousand}. The isotope data of submarine basalts suggest preferential removal of {sup 6}Li from seawater into alteration minerals during low temperature weathering. The {delta}{sup 6}Li values of two hydrothermal solutions from Guaymas Basin were found to be {minus}5{per thousand} and {minus}10{per thousand}. The results can be interpreted as the net effect of Li addition from basalt and sediments and incorporation in hydrothermal precipitates as the hydrothermal fluids interact with basin sediments. The observed enrichment of {sup 7}Li in seawater relative to submarine hydrothermal solutions, its principal Li input, is tentatively attributed to isotopic fractionation associated with low temperature alteration of sea floor basalt and incorporation in authigenic sediments. It appears that the Li isotope system may have characteristics that can resolve the mass balance of Li in the ocean.

  15. The carbon and nitrogen isotopic composition of ureilites Implications for their genesis

    NASA Astrophysics Data System (ADS)

    Grady, M. M.; Wright, I. P.; Swart, P. K.; Pillinger, C. T.

    1985-04-01

    Stepped combustion is used to determine C and N isotopic compositions in 14 and 5 ureilites, respectively. The results are presented in tables and graphs and characterized in detail. Relatively constant values of delta-(C-13) are found at 500-1000 C in each meteorite, indicating that the diamond components formed from the graphite components under conditions such as impact which did not cause isotopic fractionation. Among the ureilites, two groups with delta-(C-13) near -10 and -2 per mil are identified and found to correspond to the groups identified by Berkley et al. (1980) on the basis of the Fe content of their olivine components; this finding suggests formation from more than one ureilite parent body. Wide variations are found in the N isotopic compositions, with N abundances ranging from 25 to 150 ppm and much lower C/N ratios than in carbonaceous chondrites.

  16. Controls on the distribution and isotopic composition of helium in deep ground-water flows

    USGS Publications Warehouse

    Zhao, X.; Fritzel, T.L.B.; Quinodoz, H.A.M.; Bethke, C.M.; Torgersen, T.

    1998-01-01

    The distribution and isotopic composition of helium in sedimentary basins can be used to interpret the ages of very old ground waters. The piston-flow model commonly used in such interpretation, how ever, does not account for several important factors and as such works well only in very simple flow regimes. In this study of helium transport in a hypothetical sedimentary basin, we develop a numerical model that accounts for the magnitude and distribution of the basal helium flux, hydrodynamic dispersion, and complexities in flow regimes such as subregional flow cells. The modeling shows that these factors exert strong controls on the helium distribution and isotopic composition. The simulations may provide a basis for more accurate interpretations of observed helium concentrations and isotopic ratios in sedimentary basins.

  17. Isotopic composition analysis and age dating of uranium samples by high resolution gamma ray spectrometry

    NASA Astrophysics Data System (ADS)

    Apostol, A. I.; Pantelica, A.; Sima, O.; Fugaru, V.

    2016-09-01

    Non-destructive methods were applied to determine the isotopic composition and the time elapsed since last chemical purification of nine uranium samples. The applied methods are based on measuring gamma and X radiations of uranium samples by high resolution low energy gamma spectrometric system with planar high purity germanium detector and low background gamma spectrometric system with coaxial high purity germanium detector. The "Multigroup γ-ray Analysis Method for Uranium" (MGAU) code was used for the precise determination of samples' isotopic composition. The age of the samples was determined from the isotopic ratio 214Bi/234U. This ratio was calculated from the analyzed spectra of each uranium sample, using relative detection efficiency. Special attention is paid to the coincidence summing corrections that have to be taken into account when performing this type of analysis. In addition, an alternative approach for the age determination using full energy peak efficiencies obtained by Monte Carlo simulations with the GESPECOR code is described.

  18. Isotopic composition of lead and strontium from Ascension and Gough Islands

    USGS Publications Warehouse

    Gast, P.W.; Tilton, G.R.; Hedge, C.

    1964-01-01

    Isotopic composition of lead and strontium has been determined in a series of rock samples from two islands on the Mid-Atlantic Ridge. Both inter-and intra-island variations exist in the abundance of radiogenic isotopes of both elements. Lead from basalt of Ascension Island has a Pb206-Pb 204 ratio of 19.5, while the corresponding ratio at Gough Island is only 18.4. The Pb208-Pb204 ratios from the two islands do not differ. Conversely, strontium from basalt of Ascension Island is less radiogenic than that from Gough Island basalts. The trachytes of both islands have lead and strontium that is more radiogenic than that found in the basalts. The inter-island differences indicate the existence of regional variations in the uranium-lead and rubidium-strontium ratios of the upper mantle source of these rocks and show that isotope compositions are a means for investigating chemical heterogeneities in the mantle.

  19. Constraints on Galactic Cosmic-Ray Origins from Elemental and Isotopic Composition Measurements

    NASA Technical Reports Server (NTRS)

    Binns, W. R.; Christian, E. R.; Cummings, A. C.; deNolfo, G. A.; Israel, M. H.; Leske, R. A.; Mewaldt, R. A,; Stone, E. C.; vonRosevinge, T. T.; Wiedenbeck, M. E.

    2013-01-01

    The most recent measurements by the Cosmic Ray Isotope Spectrometer (CRIS) aboard the Advanced Composition Explorer (ACE) satellite of ultra-heavy cosmic ray isotopic and elemental abundances will be presented. A range of isotope and element ratios, most importantly Ne-22/Ne-20, Fe-58/Fe-56, and Ga-31/Ge -32 show that the composition is consistent with source material that is a mix of approx 80% ISM (with Solar System abundances) and 20% outflow/ejecta from massive stars. In addition, our data show that the ordering of refractory and volatile elements with atomic mass is greatly improved when compared to an approx 80%/20% mix rather than pure ISM, that the refractory and volatile elements have similar slopes, and that refractory elements are preferentially accelerated by a factor of approx 4. We conclude that these data are consistent with an OB association origin of GCRs.

  20. Sulphur isotopic compositions of deep-sea hydrothermal vent animals

    NASA Technical Reports Server (NTRS)

    Fry, B.; Gest, H.; Hayes, J. M.

    1983-01-01

    The S-34/S-32 ratios of tissues from vestimentiferan worms, brachyuran crabs, and giant clams living around deep hydrothermal vents are reported. Clean tissues were dried, ground, suspended in 0.1 M LiCl, shaken twice at 37 C to remove seawater sulfates, dried at 60 C, combusted in O2 in a Parr bomb. Sulfur was recovered as BaSO4, and the isotopic abundances in SO2 generated by thermal decomposition of 5-30-mg samples were determined using an isotope-ratio mass spectrometer. The results are expressed as delta S-34 and compared with values measured in seawater sulfates and in normal marine fauna. The values ranged from -4.7 to 4.7 per thousand, comparable to vent sulfide minerals (1.3-4.1 per thousand) and distinct from seawater sulfates (20.1 per thousand) and normal marine fauna (about 13-20 per thousand). These results indicate that vent sulfur rather than seawater sulfur is utilized by these animals, a process probably mediated by chemoautotrophic bacteria which can use inorganic sulfur compounds as energy sources.

  1. The isotopic composition of methane in polar ice cores

    NASA Technical Reports Server (NTRS)

    Craig, H.; Chou, C. C.; Welhan, J. A.; Stevens, C. M.; Engelkemeir, A.

    1988-01-01

    Air bubbles in polar ice cores indicate that about 300 years ago the atmospheric mixing ratio of methane began to increase rapidly. Today the mixing ratio is about 1.7 parts per million by volume, and, having doubled once in the past several hundred years, it will double again in the next 60 years if current rates continue. Carbon isotope ratios in methane up to 350 years in age have been measured with as little as 25 kilograms of polar ice recovered in 4-meter-long ice-core segments. The data show that: (1) in situ microbiology or chemistry has not altered the ice-core methane concentrations, and (2) that the carbon-13 to carbon-12 ratio of atmospheric CH4 in ice from 100 years and 300 years ago was about 2 per mil lower than at present. Atmospheric methane has a rich spectrum of isotopic sources: the ice-core data indicate that anthropogenic burning of the earth's biomass is the principal cause of the recent C-13H4 enrichment, although other factors may also contribute.

  2. [Isotopic composition of the delta-18O--delta-13C from the otoliths of reef fish from Taiaro (Tuamotu, French Polynesia): isotopic and biological implications].

    PubMed

    Blamart, Dominique; Escoubeyrou, Karine; Juillet-Leclerc, Anne; Ouahdi, Rabia; Lecomte-Finiger, Raymonde

    2002-02-01

    Nuclei (larval stage) and outer parts (adult stage) of fish otoliths from the Taiaro closed lagoon (French Polynesia) and adjacent ocean have been analysed for the C-O isotopic compositions. delta 18O values of the nuclei of both populations indicate that isotopic equilibrium is reached. This implies that the lagoonal fish population has done its complete biological cycle in the lagoon and represents an adaptation in a closed system. delta 18O values of the outer parts show a slight isotopic disequilibrium (< 0.2@1000) interpreted in term of vital effect. All the delta 13C values exhibit a strong isotopic disequilibrium related to metabolic activity. PMID:11980181

  3. Effect of photosynthetic light dosage on carbon isotope composition in the coral skeleton: Long-term culture of Porites spp.

    NASA Astrophysics Data System (ADS)

    Omata, Tamano; Suzuki, Atsushi; Sato, Takanori; Minoshima, Kayo; Nomaru, Eriko; Murakami, Akio; Murayama, Shohei; Kawahata, Hodaka; Maruyama, Tadashi

    2008-06-01

    Whereas the oxygen isotope ratio of the coral skeleton is used for reconstruction of past information on seawater, the carbon isotope ratio is considered a proxy for physiological processes, principally photosynthesis and respiration. However, the fractionation of carbon isotopes in biogenic carbonate such as coral skeleton is still unclear. We conducted a long-term culture experiment of Porites spp. corals at different light dosages (light intensity, 100, 300, or 500 μmol m-2 s-1; daily light period, 10 or 12 h) at 25 ± 0.6°C to examine the contribution of photosynthetic activity to skeletal carbon isotope composition. Corals were grown in sand-filtered seawater and not fed; thus, they subsisted from photosynthesis of symbiotic algae. As the daily dose of photosynthetically active radiation increased, the rate of annual extension also increased. Mean isotope compositions shifted; the carbon isotope compositions (δ13C) became heavier and the oxygen isotope compositions (δ18O) became lighter at higher radiation dose. Skeletal δ18O decrease coincided with increasing skeletal growth rate, indicating the influence of so-called kinetic isotope effects. The observed δ13C increase should be subject to both kinetic and metabolic isotope effects, with the latter reflecting skeletal δ13C enrichment due to photosynthesis by symbiotic algae. Using a vector approach in the δ13C-δ18O plane, we discriminated between kinetic and metabolic isotope effects on δ13C. The calculated δ13C changes from metabolic isotope effects were light dose dependent. The δ13C fractionation curve related to metabolic isotope effects is very similar to the photosynthesis-irradiance curve, indicating the direct contribution of photosynthetic activity to metabolic isotope effects. In contrast, δ13C fractionation related to kinetic isotope effects gradually increased as the growth rate increased. Our experiment demonstrated that the kinetic and metabolic isotope effects in coral skeleton

  4. Stable Isotope Composition of Carbonates Formed in Low-Temperature Terrestrial Environments as Martian Analogs

    NASA Astrophysics Data System (ADS)

    Socki, R. A.; Gibson, E. K., Jr.; Perry, E. C., Jr.; Galindo, C.; Golden, D. C.; Ming, D. W.; McKay, G. A.

    2004-03-01

    We report the C and O isotope composition of carbonate minerals that formed in two low-temperature environments. Results show an overall depletion of ^18O and ^13C as a function of the extent of meteoric diagenesis. These data are used as analogs to carbonates that have been found in ALH84001.

  5. POSSIBLE INFLUENCE OF HYDROGEN CONCENTRATION ON MICROBIAL METHANE STABLE HYDROGEN ISOTOPIC COMPOSITION

    EPA Science Inventory

    Factors affecting the stable hydrogen isotopic composition (6D) of important sources of microbial methane to the atmosphere include oxidation, methanogenic precursor (e.g., acetate vs. CO2/H2), and the 6D of the environmental water. ariations in hydrogen gas concentrations or rat...

  6. The atomic weight and isotopic composition of boron and their variation in nature

    SciTech Connect

    Holden, N.E.

    1993-08-01

    The boron isotopic composition and atomic weight value and their variation in nature are reviewed. Questions are raised about the previously recommended value and the uncertainty for the atomic weight. The problem of what constitutes an acceptable range for normal material and what should then be considered geologically exceptional is discussed. Recent measurements make some previous decisions in need of re-evaluation.

  7. Isotopic composition of lead in oceanic basalt and its implication to mantle evolution

    USGS Publications Warehouse

    Tatsumoto, M.

    1978-01-01

    New data are given in this report for (1) Pb isotopic compositions and U, Th, and Pb concentrations of basalts from the island of Hawaii; (2) redetermined Pb isotopic compositions of some abyssal tholeiites; and (3) U, Th, and Pb concentrations of altered and fresh abyssal basalts, and basalt genesis and mantle evolution are discussed. The Th U ratios of abyssal and Japanese tholeiites are distinctly lower than those of tholeiites and alkali basalts from other areas. It is thought that these low values reflect a part of the mantle depleted in large ionic lithophile elements. Thus a mantle evolution model is presented, in which Th U ratios of the depleted zone in the mantle have decreased to ???2, and U Pb ratios have increased, showing an apparent ???1.5-b.y. isochron trend in the 207Pb/204Pb vs. 206Pb/204Pb plot. The Pb isotopic compositions of basalts from the island of Hawaii are distinct for each of the five volcanoes, and within each volcano, Pb's of tholeiites and alkali basalts are similar. An interaction between partially melted material (hot plume?) of the asthenosphere and the lithosphere is suggested to explain the trend in the Pb isotopic compositions of Hawaiian basalts. ?? 1978.

  8. Nitrogen sources and cycling in the San Francisco Bay estuary: A nitrate dual isotopic composition approach

    USGS Publications Warehouse

    Wankel, Scott D.; Kendall, C.; Francis, C.A.; Paytan, A.

    2006-01-01

    We used the dual isotopic composition of nitrate (??15N and ??18O) within the estuarine system of San Francisco (SF) Bay, California, to explore the utility of this approach for tracing sources and cycling of nitrate (NO3-). Surface water samples from 49 sites within the estuary were sampled during July-August 2004. Spatial variability in the isotopic composition suggests that there are multiple sources of nitrate to the bay ecosystem including seawater, several rivers and creeks, and sewage effluent. The spatial distribution of nitrate from these sources is heavily modulated by the hydrodynamics of the estuary. Mixing along the estuarine salinity gradient is the main control on the spatial variations in isotopic composition of nitrate within the northern arm of SF Bay. However, the nitrate isotopic composition in the southern arm of SF Bay exhibited a combination of source mixing and phytoplankton drawdown due mostly to the long residence time during the summer study period. Very low ?? 18ONO3 values (as low as -5.0???) at the Sacramento-San Joaquin River delta region give rise to a wide range of ??18ONO3 values in the SF Bay system. The range in ??18ONO3 values is more than twice that of (??15NNO3, suggesting that ??18O NO3 is an even more sensitive tool for tracing nitrate sources and cycling than ??15NNO3. ?? 2006, by the American Society of Limnology and Oceanography, Inc.

  9. Habitat use and trophic position effects on contaminant bioaccumulation in fish indicated by stable isotope composition

    EPA Science Inventory

    The objective of our study was to determine the relationship between fish tissue stable isotope composition and total mercury or polychlorinated biphenyl (PCB) concentrations in a Great Lakes coastal food web. We sampled two resident fishes, Yellow Perch (Perca flavescens) and Bl...

  10. Molecular Paleohydrology: Interpreting the Hydrogen-Isotopic Composition of Lipid Biomarkers from Photosynthesizing Organisms

    NASA Astrophysics Data System (ADS)

    Sachse, Dirk; Billault, Isabelle; Bowen, Gabriel J.; Chikaraishi, Yoshito; Dawson, Todd E.; Feakins, Sarah J.; Freeman, Katherine H.; Magill, Clayton R.; McInerney, Francesca A.; van der Meer, Marcel T. J.; Polissar, Pratigya; Robins, Richard J.; Sachs, Julian P.; Schmidt, Hanns-Ludwig; Sessions, Alex L.; White, James W. C.; West, Jason B.; Kahmen, Ansgar

    2012-05-01

    Hydrogen-isotopic abundances of lipid biomarkers are emerging as important proxies in the study of ancient environments and ecosystems. A decade ago, pioneering studies made use of new analytical methods and demonstrated that the hydrogen-isotopic composition of individual lipids from aquatic and terrestrial organisms can be related to the composition of their growth (i.e., environmental) water. Subsequently, compound-specific deuterium/hydrogen (D/H) ratios of sedimentary biomarkers have been increasingly used as paleohydrological proxies over a range of geological timescales. Isotopic fractionation observed between hydrogen in environmental water and hydrogen in lipids, however, is sensitive to biochemical, physiological, and environmental influences on the composition of hydrogen available for biosynthesis in cells. Here we review the factors and processes that are known to influence the hydrogen-isotopic compositions of lipids—especially n-alkanes—from photosynthesizing organisms, and we provide a framework for interpreting their D/H ratios from ancient sediments and identify future research opportunities.

  11. Soil moisture effects on the carbon isotopic composition of soil respiration

    EPA Science Inventory

    The carbon isotopic composition ( 13C) of recently assimilated plant carbon is known to depend on water-stress, caused either by low soil moisture or by low atmospheric humidity. Air humidity has also been shown to correlate with the 13C of soil respiration, which suggests indir...

  12. Effects of diagenesis on strontium, carbon, nitrogen and oxygen concentration and isotopic composition of bone

    NASA Astrophysics Data System (ADS)

    Nelson, Bruce K.; Deniro, Michael J.; Schoeninger, Margaret J.; De Paolo, Donald J.; Hare, P. E.

    1986-09-01

    Paleodietary analysis based on variations in the trace element and stable isotopic composition of inorganic and organic phases in fossil bone depends on the assumption that measured values reflect in vivo values. To test for postmortem alteration, we measured 87Sr /86Sr , 13C /12C , 18O /16O and 15N /14N ratios and Sr concentrations in modern and prehistoric (610 to 5470 yr old) bones of animals with marine or terrestrial diets from Greenland. Bones from modern terrestrial feeders have substantially lower Sr concentrations and more radiogenic 87Sr /86Sr ratios than those from modern marine feeders. This contrast was not preserved in the prehistoric samples, which showed almost complete overlap for both Sr concentration and isotopic composition in bones from the two types of animals. Leaching experiments, X-ray diffraction analysis and infrared spectroscopy indicate that alteration of the Sr concentration and isotopic composition in prehistoric bone probably results from nearly complete exchange with groundwater. Oxygen isotope ratios in fossil apatite carbonate also failed to preserve the original discrimination between modern terrestrial and marine feeders. The C isotope ratio of apatite carbonate did not discriminate between animals with marine or terrestrial diets in the modern samples. Even so, the ranges of apatite δ 13C values in prehistoric bone are more scattered than in modern samples for both groups, suggesting alteration had occurred. δ 13C and δ 15N values of collagen in modern bone are distinctly different for the two feeding types, and this distinction is preserved in most of the prehistoric samples. Our results suggest that postmortem alteration of dietary tracers in the inorganic phases of bone may be a problem at all archaeological sites and must be evaluated in each case. While collagen analyzed in this study was resistant to alteration, evaluation of the possibility of diagenetic alteration of its isotopic composition in bones from other

  13. Chemical and stable-radiogenic isotope compositions of Polatlı-Haymana thermal waters (Ankara, Turkey)

    NASA Astrophysics Data System (ADS)

    Akilli, Hafize; Mutlu, Halim

    2016-04-01

    Complex tectono-magmatic evolution of the Anatolian land resulted in development of numerous geothermal areas through Turkey. The Ankara region in central Anatolia is surrounded by several basins which are filled with upper Cretaceous-Tertiary sediments. Overlying Miocene volcanics and step faulting along the margins of these basins played a significant role in formation of a number of low-enthalpy thermal waters. In this study, chemical and isotopic compositions of Polatlı and Haymana geothermal waters in the Ankara region are investigated. The Polatlı-Haymana waters with a temperature range of 24 to 43 °C are represented by Ca-(Na)-HCO3 composition implying derivation from carbonate type reservoir rocks. Oxygen-hydrogen isotope values of the waters are conformable with the Global Meteoric Water Line and point to a meteoric origin. The carbon isotopic composition in dissolved inorganic carbon (DIC) of the studied waters is between -21.8 and -1.34 permil (vs. VPDB). Marine carbonates and organic rocks are the main sources of carbon. There is a high correlation between oxygen (3.7 to 15.0 permil; VSMOW) and sulfur (-9.2 to 19.5 permil; VCDT) isotope compositions of sulfate in waters. The mixing of sulfate from dissolution of marine carbonates and terrestrial evaporite units is the chief process behind the observed sulfate isotope systematics of the samples. 87Sr/86Sr ratios of waters varying from 0.705883 to 0.707827 are consistent with those of reservoir rocks. The temperatures calculated by SO4-H2O isotope geothermometry are between 81 and 138 °C nearly doubling the estimates from chemical geothermometers.

  14. Stable water isotopic composition of the Antarctic subglacial Lake Vostok: implications for understanding the lake's hydrology.

    PubMed

    Ekaykin, Alexey A; Lipenkov, Vladimir Y; Kozachek, Anna V; Vladimirova, Diana O

    2016-01-01

    We estimated the stable isotopic composition of water from the subglacial Lake Vostok using two different sets of samples: (1) water frozen on the drill bit immediately after the first lake unsealing and (2) water frozen in the borehole after the unsealing and re-drilled one year later. The most reliable values of the water isotopic composition are: -59.0 ± 0.3 ‰ for oxygen-18, -455 ± 1 ‰ for deuterium and 17 ± 1 ‰ for d-excess. This result is also confirmed by the modelling of isotopic transformations in the water which froze in the borehole, and by a laboratory experiment simulating this process. A comparison of the newly obtained water isotopic composition with that of the lake ice (-56.2 ‰ for oxygen-18, -442.4 ‰ for deuterium and 7.2 ‰ for d-excess) leads to the conclusion that the lake ice is very likely formed in isotopic equilibrium with water. In turn, this means that ice is formed by a slow freezing without formation of frazil ice crystals and/or water pockets. This conclusion agrees well with the observed physical and chemical properties of the lake's accreted ice. However, our estimate of the water's isotopic composition is only valid for the upper water layer and may not be representative for the deeper layers of the lake, so further investigations are required. PMID:26862787

  15. Absolute Quantification of Prion Protein (90-231) Using Stable Isotope-Labeled Chymotryptic Peptide Standards in a LC-MRM AQUA Workflow

    NASA Astrophysics Data System (ADS)

    Sturm, Robert; Sheynkman, Gloria; Booth, Clarissa; Smith, Lloyd M.; Pedersen, Joel A.; Li, Lingjun

    2012-09-01

    Substantial evidence indicates that the disease-associated conformer of the prion protein (PrPTSE) constitutes the etiologic agent in prion diseases. These diseases affect multiple mammalian species. PrPTSE has the ability to convert the conformation of the normal prion protein (PrPC) into a β-sheet rich form resistant to proteinase K digestion. Common immunological techniques lack the sensitivity to detect PrPTSE at subfemtomole levels, whereas animal bioassays, cell culture, and in vitro conversion assays offer higher sensitivity but lack the high-throughput the immunological assays offer. Mass spectrometry is an attractive alternative to the above assays as it offers high-throughput, direct measurement of a protein's signature peptide, often with subfemtomole sensitivities. Although a liquid chromatography-multiple reaction monitoring (LC-MRM) method has been reported for PrPTSE, the chemical composition and lack of amino acid sequence conservation of the signature peptide may compromise its accuracy and make it difficult to apply to multiple species. Here, we demonstrate that an alternative protease (chymotrypsin) can produce signature peptides suitable for a LC-MRM absolute quantification (AQUA) experiment. The new method offers several advantages, including: (1) a chymotryptic signature peptide lacking chemically active residues (Cys, Met) that can confound assay accuracy; (2) low attomole limits of detection and quantitation (LOD and LOQ); and (3) a signature peptide retaining the same amino acid sequence across most mammals naturally susceptible to prion infection as well as important laboratory models. To the authors' knowledge, this is the first report on the use of a non-tryptic peptide in a LC-MRM AQUA workflow.

  16. Multiple sulfur isotope composition of oxidized Samoan melts and the implications of a sulfur isotope 'mantle array' in chemical geodynamics

    NASA Astrophysics Data System (ADS)

    Labidi, J.; Cartigny, P.; Jackson, M. G.

    2015-05-01

    To better address how subducted protoliths drive the Earth's mantle sulfur isotope heterogeneity, we report new data for sulfur (S) and copper (Cu) abundances, S speciation and multiple S isotopic compositions (32S, 33S, 34S, 36S) in 15 fresh submarine basaltic glasses from the Samoan archipelago, which defines the enriched-mantle-2 (EM2) endmember. Bulk S abundances vary between 835 and 2279 ppm. About 17 ± 11% of sulfur is oxidized (S6+) but displays no consistent trend with bulk S abundance or any other geochemical tracer. The S isotope composition of both dissolved sulfide and sulfate yield homogeneous Δ33S and Δ36S values, within error of Canyon Diablo Troilite (CDT). In contrast, δ34S values are variable, ranging between +0.11 and +2.79‰ (±0.12‰ 1σ) for reduced sulfur, whereas oxidized sulfur values vary between +4.19 and +9.71‰ (±0.80‰, 1σ). Importantly, δ34S of the reduced S pool correlates with the 87Sr/86Sr ratios of the glasses, in a manner similar to that previously reported for South-Atlantic MORB, extending the trend to δ34S values up to + 2.79 ± 0.04 ‰, the highest value reported for undegassed oceanic basalts. As for EM-1 basalts from the South Atlantic ridge, the linear δ34S-87Sr/86Sr trend requires the EM-2 endmember to be relatively S-rich, and only sediments can account for these isotopic characteristics. While many authors argue that both the EM-1 and EM-2 mantle components record subduction of various protoliths (e.g. upper or lower continental crust, lithospheric mantle versus intra-metasomatized mantle, or others), it is proposed here that they primarily reflect sediment recycling. Their distinct Pb isotope variation can be accounted for by varying the proportion of S-poor recycled oceanic crust in the source of mantle plumes.

  17. Isotopic composition and neutronics of the Okelobondo natural reactor

    NASA Astrophysics Data System (ADS)

    Palenik, Christopher Samuel

    The Oklo-Okelobondo and Bangombe uranium deposits, in Gabon, Africa host Earth's only known natural nuclear fission reactors. These 2 billion year old reactors represent a unique opportunity to study used nuclear fuel over geologic periods of time. The reactors in these deposits have been studied as a means by which to constrain the source term of fission product concentrations produced during reactor operation. The source term depends on the neutronic parameters, which include reactor operation duration, neutron flux and the neutron energy spectrum. Reactor operation has been modeled using a point-source computer simulation (Oak Ridge Isotope Generation and Depletion, ORIGEN, code) for a light water reactor. Model results have been constrained using secondary ionization mass spectroscopy (SIMS) isotopic measurements of the fission products Nd and Te, as well as U in uraninite from samples collected in the Okelobondo reactor zone. Based upon the constraints on the operating conditions, the pre-reactor concentrations of Nd (150 ppm +/- 75 ppm) and Te (<1 ppm) in uraninite were estimated. Related to the burnup measured in Okelobondo samples (0.7 to 13.8 GWd/MTU), the final fission product inventories of Nd (90 to 1200 ppm) and Te (10 to 110 ppm) were calculated. By the same means, the ranges of all other fission products and actinides produced during reactor operation were calculated as a function of burnup. These results provide a source term against which the present elemental and decay abundances at the fission reactor can be compared. Furthermore, they provide new insights into the extent to which a "fossil" nuclear reactor can be characterized on the basis of its isotopic signatures. In addition, results from the study of two other natural systems related to the radionuclide and fission product transport are included. A detailed mineralogical characterization of the uranyl mineralogy at the Bangombe uranium deposit in Gabon, Africa was completed to improve

  18. New approach to global barium cycle understanding: barium isotopic composition of marine carbonates and seawater.

    NASA Astrophysics Data System (ADS)

    Pretet, Chloé; Nägler, Thomas F.; Reynaud, Stéphanie; de Lange, Gert J.; Turpin, Mélanie; Immenhauser, Adrian; Böttcher, Michael E.; Samankassou, Elias

    2013-04-01

    In this communication we present the Ba isotope fractionation (delta137/134Ba) study on marine carbonates and seawater, initiated to gain a first order view of the marine Ba isotope cycle. A special focus is the question whether the nutrient type distribution of Ba in the water column, as well as different Ba sources, are reflected in Ba isotope ratios of carbonate archives. The approach ultimately aims to provide an improved Ba based paleonutrient proxy. The data set is composed of carbonates (micrites and limestone standard), coral skeleton and seawater (IAPSO standard and Mediterranean seawater). Part of the corals were cultured in monitored environments (CSM, Monaco) others originate from natural environments (shallow and warm water corals from the Bahamas/Florida and cold water corals from the Norwegian shelf). The analytical procedure includes the application of a 130Ba/135Ba double spike, a cation exchange column followed by isotope measurements on a Nu Instruments Multicollector ICP-MS. The Ba fractionation of the samples is compared to a Ba nitrate standard solution and a standard natural limestone BSC-CRM 393 (0.05 ± 0.04 ‰, 2SEM). No isotopic fractionation has been observed in the limestone standard and micrites (N=8) (-0.01 ± 0.04 ‰, 2SEM) compared to the Ba nitrate standard. On the contrary, coral skeletons show a significant positive fractionation (mean = 0.4 ± 0.05 ‰, 2 SEM). No significant difference was found between different cultured coral species. Thus no species-specific fractionation is identified within the same environmental conditions. Diagenetic influence on Ba isotopic composition was further tested on 5 natural samples with varying calcite to aragonite ratios (0 to 0.3). No significant effect was observed. Moreover, the Ba isotope composition seems independant from the Ba concentration in the studied coral skeleton, within our measurement resolution. Seawater isotopic composition (-0.05 ± 0.07 ‰, 2SD) is lighter than coral

  19. The silicon isotope composition of enstatite meteorites and their importance as proto-Earth components

    NASA Astrophysics Data System (ADS)

    Savage, P. S.; Moynier, F.

    2012-12-01

    Of the major primitive meteorite groups, the enstatite chondrites (EC) are the most chemically dissimilar to terrestrial composition [1]. This might preclude them as major components of the proto-Earth; however, for many isotope systems (most notably oxygen, ref. 2), enstatite chondrites and the Earth are compositionally alike. This has led some authors to infer that a significant proportion of Earth accreted from such meteorites [3]. In contrast to many isotope systems, silicon (Si) apparently exhibits significant mass-dependent variations between EC and Bulk Silicate Earth (BSE), which has been used as further evidence against the EC Earth model [4]. However, these conclusions are based on scant data, only 8 analyses of 6 separate meteorites. Here we present a comprehensive investigation into the Si isotope composition of enstatite chondrites and their differentiated counterparts, the aubrites. Our results confirm that enstatite meteorites have Si isotope compositions that are significantly lighter than both ordinary and carbonaceous chondrites and BSE; as such, the EC are the lightest macroscale objects, relative to Si isotopes, so far analysed from the solar system. The data also show that EH (high iron) chondrites have significantly lighter Si isotope compositions than EL (low iron) chondrites, supporting the assertion that these meteorite groups formed on separate bodies. Silicon isotope analyses of the metal-free components of EH and EL chondrites are identical, within error, to each other and with carbonaceous/ordinary chondrite bulk composition [5]. From this we infer that elemental fractionation in the nebular gas is not the cause of the light Si isotope enrichment in enstatite chondrites. A good negative correlation between bulk δ30Si and Si content in kamacite (Fe-Ni metal) in enstatite chondrites indicates that the presence of isotopically light Si in the metal phase (as the result of formation under reducing conditions) is the principle cause of the

  20. The uranium isotopic composition of the Earth and the Solar System

    NASA Astrophysics Data System (ADS)

    Goldmann, Alexander; Brennecka, Gregory; Noordmann, Janine; Weyer, Stefan; Wadhwa, Meenakshi

    2015-01-01

    Recent high-precision mass spectrometric studies of the uranium isotopic composition of terrestrial and meteoritic materials have shown significant variation in the 238U/235U ratio, which was previously assumed to be invariant (=137.88). In this study, we have investigated 27 bulk meteorite samples from different meteorite groups and types, including carbonaceous (CM1 and CV3), enstatite (EH4) and ordinary (H-, L-, and LL-) chondrites, as well as a variety of achondrites (angrites, eucrites, and ungrouped) to constrain the distribution of U isotopic heterogeneities and to determine the average 238U/235U for the Solar System. The investigated bulk meteorites show a range in 238U/235U between 137.711 and 137.891 (1.3‰) with the largest variations among ordinary chondrites (OCs). However, the U isotope compositions of 20 of the 27 meteorites analyzed here overlap within analytical uncertainties with the narrow range defined by terrestrial basalts (137.778-137.803), which are likely the best representatives for the U isotope composition of the bulk silicate Earth. Furthermore, the average 238U/235U of all investigated meteorite groups overlaps with that of terrestrial basalts (137.795 ± 0.013). The bulk meteorite samples studied here do not show a negative correlation of 238U/235U with Nd/U or Th/U (used as proxies for the Cm/U ratio), as would be expected if radiogenic 235U was generated by the decay of extant 247Cm in the early Solar System. Rather, ordinary chondrites show a positive correlation of 238U/235U with Nd/U and with 1/U. The following conclusions can be drawn from this study: (1) The Solar System has a broadly homogeneous U isotope composition, and bulk samples of only a limited number of meteorites display detectable U isotope variations; (2) Bulk planetary differentiation has no significant effect on the 238U/235U ratio since the Earth, achondrites, and chondrites have indistinguishable U isotope compositions in average. (3) The cause of U isotopic

  1. Oxygenation of a Cryogenian ocean (Nanhua Basin, South China) revealed by pyrite Fe isotope compositions

    NASA Astrophysics Data System (ADS)

    Zhang, Feifei; Zhu, Xiangkun; Yan, Bin; Kendall, Brian; Peng, Xi; Li, Jin; Algeo, Thomas J.; Romaniello, Stephen

    2015-11-01

    The nature of ocean redox chemistry between the Cryogenian Sturtian and Marinoan glaciations (ca. 663-654 Ma) is important for understanding the relationship between environmental conditions and the subsequent emergence and expansion of early animals. The Cryogenian-to-Ediacaran stratigraphic succession of the Nanhua Basin in South China provides a nearly complete sedimentary record of the Cryogenian, including a continuous record of interglacial sedimentation. Here, we present a high-resolution pyrite Fe isotope record for a ∼120-m-long drill-core (ZK105) through Sturtian glacial diamictites and the overlying interglacial sediments in the Nanhua Basin to explore changes in marine chemistry during the late Cryogenian. Our pyrite Fe isotope profile exhibits significant stratigraphic variation: Interval I, comprising middle to upper Tiesi'ao diamictites (correlative with the Sturtian glaciation), is characterized by light, modern seawater-like Fe isotope compositions; Interval II, comprising uppermost Tiesi'ao diamictites and the basal organic-rich Datangpo Formation, is characterized by an abrupt shift to heavier Fe isotope compositions; and Interval III, comprising organic-poor grey shales in the middle Datangpo Formation, is characterized by the return of lighter, seawater-like Fe isotope compositions. We infer that Interval I pyrite was deposited in a predominantly anoxic glacial Nanhua Basin through reaction of dissolved Fe2+ and H2S mediated by microbial sulfate reduction (MSR). The shift to heavier pyrite Fe isotope values in Interval II is interpreted as partial oxidation of ferrous iron to ferric iron and subsequent near-quantitative reduction and transformation of Fe-oxyhydroxides to pyrite through coupling with oxidation of organic matter in the local diagenetic environment. In Interval III, near-quantitative oxidation of ferrous iron to Fe-oxyhydroxides followed by near-quantitative reduction and conversion to pyrite in the local diagenetic environment

  2. Absolute Zero

    NASA Astrophysics Data System (ADS)

    Donnelly, Russell J.; Sheibley, D.; Belloni, M.; Stamper-Kurn, D.; Vinen, W. F.

    2006-12-01

    Absolute Zero is a two hour PBS special attempting to bring to the general public some of the advances made in 400 years of thermodynamics. It is based on the book “Absolute Zero and the Conquest of Cold” by Tom Shachtman. Absolute Zero will call long-overdue attention to the remarkable strides that have been made in low-temperature physics, a field that has produced 27 Nobel Prizes. It will explore the ongoing interplay between science and technology through historical examples including refrigerators, ice machines, frozen foods, liquid oxygen and nitrogen as well as much colder fluids such as liquid hydrogen and liquid helium. A website has been established to promote the series: www.absolutezerocampaign.org. It contains information on the series, aimed primarily at students at the middle school level. There is a wealth of material here and we hope interested teachers will draw their student’s attention to this website and its substantial contents, which have been carefully vetted for accuracy.

  3. Isotope variations of dissolved Zn in the Rio Grande watershed, USA: The role of adsorption on Zn isotope composition

    NASA Astrophysics Data System (ADS)

    Szynkiewicz, Anna; Borrok, David M.

    2016-01-01

    In order to better understand the factors influencing zinc (Zn) isotope composition in hydrological systems, we analyzed the δ66Zn of dissolved Zn in the streams and groundwater of the Upper and Middle Rio Grande watershed in Colorado and New Mexico, United States. The stream water samples have a wider variation of δ66Zn (-0.57 to + 0.41 ‰ relative to the JMC 3-0749-Lyon standard) than groundwater samples (-0.13 to + 0.12 ‰) and than samples from streams that are in close proximity to abandoned mining sites (+0.24 to + 0.40 ‰). Regional changes of bedrock geology, from primarily igneous rocks to primarily sedimentary rocks, have no resolvable effect on the δ66Zn of aqueous samples. Instead, an increase in water pH from 7.5 to 8.5 corresponds to a considerable decrease in the δ66Zn of dissolved Zn (R2 = - 0.37, p = 0.003, n = 22). Consequently, we link the observed Zn isotope variations to the process of adsorption of Zn onto suspended sediment and bedrock minerals (average Δ66Znadsorbed-dissolved = + 0.31 ‰). Our results are in good agreement with previous experimental and empirical studies suggesting that Zn adsorption leads to a residual dissolved pool enriched in light Zn isotopes. Given that anthropogenic Zn sources can also be responsible for lowering of δ66Zn, and may overlap with the pH/adsorption effect on δ66Zn, the latter needs to be carefully considered in future studies to differentiate between natural and anthropogenic factors influencing Zn isotopes in this and other aquatic systems.

  4. The Influence of Kinetic Growth Factors on the Clumped Isotope Composition of Calcite

    NASA Astrophysics Data System (ADS)

    Hunt, J. D.; Watkins, J. M.; Tripati, A.; Ryerson, F. J.; DePaolo, D. J.

    2014-12-01

    Clumped isotope paleothermometry is based on the association of 13C and 18O within carbonate minerals. Although the influence of temperature on equilibrium 13C-18O bond ordering has been studied, recent oxygen isotope studies of inorganic calcite demonstrate that calcite grown in laboratory experiments and in many natural settings does not form in equilibrium with water. It is therefore likely that the carbon and clumped isotope composition of these calcite crystals are not representative of true thermodynamic equilibrium. To isolate kinetic clumped isotope effects that arise at the mineral-solution interface, clumped isotopic equilibrium of DIC species must be maintained. This can be accomplished by dissolving the enzyme carbonic anhydrase (CA) into the solution, thereby reducing the time required for isotopic equilibration of DIC species by approximately two orders of magnitude between pH 7.7 and 9.3. We conduct calcite growth experiments aimed specifically at measuring the pH-dependence of kinetic clumped isotope effects during non-equilibrium precipitation of calcite. We precipitated calcite from aqueous solution at a constant pH and controlled supersaturation over the pH range 7.7-9.3 in the presence of CA. For each experiment, a gas mixture of N2 and CO2 is bubbled through a beaker of solution without seed crystals. As CO2 from the gas dissolves into solution, calcite crystals grow on the beaker walls. The pH of the solution is maintained by use of an autotitrator with NaOH as the titrant. We control the temperature, pH, the pCO2 of the gas inflow, and the gas inflow rate, and monitor the total alkalinity, the pCO2 of the gas outflow, and the amount of NaOH added. A constant crystal growth rate of ~1.6 mmol/m2/hr is maintained over all experiments. Results from these experiments are compared to predictions from a recently-developed isotopic ion-by-ion growth model of calcite. The model describes the rate, temperature and pH dependence of oxygen isotope uptake

  5. Lithium isotopic composition of the lower continental crust: A xenolith perspective

    NASA Astrophysics Data System (ADS)

    Teng, F.; McDonough, W. F.; Rudnick, R. L.; Tomascak, P. B.; Saal, A. E.

    2003-12-01

    Study of high-grade metamorphic rocks is important for understanding the lithium isotopic composition of the lower crust and determining the degree to which lithium isotopes fractionate during metamorphism. Here we present Li isotopic data for two well-characterized suites of lower crustal xenoliths from North Queesland, Australia [1, 2]. These xenoliths have average major-and trace-element compositions similar to estimates of the bulk lower continental crust, and can therefore be used to place broad constraints on its Li isotopic composition. Furthermore, the Chudleigh xenoliths are a suite of cogenetic cumulates that formed through AFC of Cenozoic basaltic magma that intruded Proterozoic lower crust, and thus may provide insight into the regional average δ 7Li of the lower crust. The samples display a large range of Li concentrations and isotopic compositions with the average, concentration-weighted δ 7Li value = 0. McBride xenoliths are enriched in Li (7 +/- 4 ppm versus 3 +/- 2 ppm) and have a larger range of δ 7Li values (-13 to +7 versus -9 to +6) than Chudleigh xenoliths, consistent with differences in lithology and genetic diversity: McBride xenoliths range from paragneisses to mafic and felsic orthogneisses whereas the Chudleigh xenoliths are mafic cumulates. Mg#, 87Sr/86Sr and 143Nd/144Nd in the Chudeigh suite correlate with δ 7Li, reflecting assimilation of isotopically light Proterozoic lower crust (δ 7Li < -9) by heavier (δ 7Li ˜ +6) mantle-derived basalt. The δ 7Li values of the lower continental crust are heterogeneous, and its average composition is similar to the upper continental crust [3] or lighter; this suggests that the continents are isotopically lighter than the mantle [4]. The isotopically light continental crust is probably derived from two processes involving fluid-rock interactions: surface weathering and metamorphic dehydration. Both processes drive the hydrosphere to heavier (+30) and bulk continental crust to lighter (-1 to 0

  6. Oxygen and nitrogen isotopic composition of nitrate in commercial fertilizers, nitric acid, and reagent salts.

    PubMed

    Michalski, Greg; Kolanowski, Michelle; Riha, Krystin M

    2015-01-01

    Nitrate is a key component of synthetic fertilizers that can be beneficial to crop production in agro-ecosystems, but can also cause damage to natural ecosystems if it is exported in large amounts. Stable isotopes, both oxygen and nitrogen, have been used to trace the sources and fate of nitrate in various ecosystems. However, the oxygen isotope composition of synthetic and organic nitrates is poorly constrained. Here, we present a study on the N and O isotope composition of nitrate-based fertilizers. The δ(15)N values of synthetic and natural nitrates were 0 ± 2 ‰ similar to the air N2 from which they are derived. The δ(18)O values of synthetic nitrates were 23 ± 3 ‰, similar to air O2, and natural nitrate fertilizer δ(18)O values (55 ± 5 ‰) were similar to those observed in atmospheric nitrate. The Δ(17)O values of synthetic fertilizer nitrate were approximately zero following a mass-dependent isotope relationship, while natural nitrate fertilizers had Δ(17)O values of 18 ± 2 ‰ similar to nitrate produced photochemically in the atmosphere. These narrow ranges of values can be used to assess the amount of nitrate arising from fertilizers in mixed systems where more than one nitrate source exists (soil, rivers, and lakes) using simple isotope mixing models. PMID:26181213

  7. Oxygen isotope composition of modern pedogenic carbonate from the southern margin of the Tibetan Plateau

    NASA Astrophysics Data System (ADS)

    Breecker, D.; Sharp, Z.; Newell, D.; Jessup, M.; Cottle, J.

    2007-12-01

    Oxygen-isotope paleoelevation estimates of large plateaus provide important geodynamic constraints on the teconic evolution of orogenic systems as well as offering insight into the dynamic feedbacks between surface uplift and regional- to global-scale climate systems. If the isotopic lapse rate (δ18O vs elevation) is known, then the oxygen isotope composition of ancient meteoric water can be used to estimate paleoelevation. The oxygen isotope composition of pedogenic carbonate preserved in paleosols has been used as a proxy for the oxygen isotope composition of soil water in order to reconstruct paleoelevation in a number of settings. Isotopic equilibrium between carbonate and water is assumed in order to calculate the δ18O value of soil water from measured δ18O values of pedogenic carbonate (δ18Opc). Uncertainties surrounding the temperature of isotopic equilibrium and the degree of evaporation of soil water limit the precision of elevation estimates from pedogenic carbonate. In this study, measurements of the oxygen isotope composition of pedogenic carbonate forming in modern soils from the Mt. Everest Region of Tibet are compared with modern meteoric water δ18O values (δ18Omw) to calibrate δ18Opc as a proxy for elevation. Pedogenic carbonate samples coating the underside of clasts were collected along depth profiles in soils at different elevations ranging from 3750 - 5200m on the southern margin of the Tibetan Plateau. Incipient soils developing in the lowest and presumably youngest river terraces were chosen for δ18Opc measurements because these are the most likely to have formed under the influence of modern precipitation. The oxygen isotope composition of modern spring and stream waters along the Bhote Kosi and Arun River were also measured in this study and agree well with previously published elevation- δ18Omw relationships for the Himalayas. Average δ18Opc values below 50 cm in the modern soils were used to calculate equilibrium δ18Omw values

  8. Nickel isotopic compositions of ferromanganese crusts and the constancy of deep ocean inputs and continental weathering effects over the Cenozoic

    NASA Astrophysics Data System (ADS)

    Gall, L.; Williams, H. M.; Siebert, C.; Halliday, A. N.; Herrington, R. J.; Hein, J. R.

    2013-08-01

    The global variability in nickel (Ni) isotope compositions in ferromanganese crusts is investigated by analysing surface samples of 24 crusts from various ocean basins by MC-ICPMS, using a double-spike for mass bias correction. Ferromanganese crusts have δ60Ni isotopic compositions that are significantly heavier than any other samples thus far reported (-0.1‰ to 0.3 ‰), with surface scrapings ranging between 0.9 ‰ and 2.5 ‰ (relative to NIST SRM986). There is no well resolved difference between ocean basins, although the data indicate somewhat lighter values in the Atlantic than in the Pacific, nor is there any evidence that the variations are related to biological fractionation, presence of different water masses, or bottom water redox conditions. Preliminary data for laterite samples demonstrate that weathering is accompanied by isotopic fractionation of Ni, which should lead to rivers and seawater being isotopically heavy. This is consistent with the slightly heavier than average isotopic compositions recorded in crusts that are sampled close to continental regions. Furthermore, the isotopic compositions of crusts growing close to a hydrothermal source are clustered around ∼ 1.5 ‰, suggesting that hydrothermal fluids entering the ocean may have a Ni isotopic composition similar to this value. Based on these data, the heavy Ni isotopic compositions of ferromanganese crusts are likely due to input of isotopically heavy Ni to the ocean from continental weathering and possibly also from hydrothermal fluids. A depth profile through one crust, CD29-2, from the north central Pacific Ocean displays large variations in Ni isotope composition (1.1 - 2.3 ‰) through the last 76 Myr. Although there may have been some redistribution of Ni associated with phosphatisation, there is no systematic difference in Ni isotopic composition between deeper, older parts and shallower, younger parts of the crust, which may suggest that oceanic sources and sinks of Ni have

  9. Coordinated Oxygen Isotopic and Petrologic Studies of CAIS Record Varying Composition of Protosolar

    NASA Technical Reports Server (NTRS)

    Simon, Justin I.; Matzel, J. E. P.; Simon, S. B.; Weber, P. K.; Grossman, L.; Ross, D. K.; Hutcheon, I. D.

    2012-01-01

    Ca-, Al-rich inclusions (CAIs) record the O-isotope composition of Solar nebular gas from which they grew [1]. High spatial resolution O-isotope measurements afforded by ion microprobe analysis across the rims and margin of CAIs reveal systematic variations in (Delta)O-17 and suggest formation from a diversity of nebular environments [2-4]. This heterogeneity has been explained by isotopic mixing between the O-16-rich Solar reservoir [6] and a second O-16-poor reservoir (probably nebular gas) with a "planetary-like" isotopic composition [e.g., 1, 6-7], but the mechanism and location(s) where these events occur within the protoplanetary disk remain uncertain. The orientation of large and systematic variations in (Delta)O-17 reported by [3] for a compact Type A CAI from the Efremovka reduced CV3 chondrite differs dramatically from reports by [4] of a similar CAI, A37 from the Allende oxidized CV3 chondrite. Both studies conclude that CAIs were exposed to distinct, nebular O-isotope reservoirs, implying the transfer of CAIs among different settings within the protoplanetary disk [4]. To test this hypothesis further and the extent of intra-CAI O-isotopic variation, a pristine compact Type A CAI, Ef-1 from Efremovka, and a Type B2 CAI, TS4 from Allende were studied. Our new results are equally intriguing because, collectively, O-isotopic zoning patterns in the CAIs indicate a progressive and cyclic record. The results imply that CAIs were commonly exposed to multiple environments of distinct gas during their formation. Numerical models help constrain conditions and duration of these events.

  10. Ca Cycle Constraints from the Ca Isotope Composition of Precambrian Sedimentary Carbonates

    NASA Astrophysics Data System (ADS)

    Blättler, C. L.; Higgins, J. A.

    2014-12-01

    The geochemical cycle of Ca in seawater is relatively straightforward - Ca is ultimately sourced from the weathering of silicates and largely removed as carbonates. Most of these carbonates are then recycled through subsequent uplift and weathering, but some are metamorphosed or returned to the mantle via subduction. Ca isotopes in sedimentary marine carbonates can provide new insights into the global Ca (and by corollary, C) cycle by constraining the flux and isotopic composition of the recycled and subducted Ca sinks on billion-year timescales. Precambrian applications of Ca isotopes have so far been limited to relatively small datasets which cover unusual, dynamic intervals of the Proterozoic. In order to address questions about long-timescale Ca cycling, Ca isotopes were measured on an extensive suite of Precambrian carbonates (n > 300) which represent environments, textures, and morphologies that are typical for their age, and whose carbon isotope values have been interpreted as reflecting precipitation from seawater. Because marine carbonates constitute the dominant geological sink for Ca, this representative sample set places specific limits on the evolution of the sedimentary and crustal Ca reservoirs and suggests further applications for Ca isotopes in Precambrian time.

  11. Stable bromine isotopic composition of methyl bromide released from plant matter

    NASA Astrophysics Data System (ADS)

    Horst, Axel; Holmstrand, Henry; Andersson, Per; Thornton, Brett F.; Wishkerman, Asher; Keppler, Frank; Gustafsson, Örjan

    2014-01-01

    Methyl bromide (CH3Br) emitted from plants constitutes a natural source of bromine to the atmosphere, and is a component in the currently unbalanced global CH3Br budget. In the stratosphere, CH3Br contributes to ozone loss processes. Studies of stable isotope composition may reduce uncertainties in the atmospheric CH3Br budget, but require well-constrained isotope fingerprints of the source end members. Here we report the first measurements of stable bromine isotopes (δ81Br) in CH3Br from abiotic plant emissions. Incubations of both KBr-fortified pectin, a ubiquitous cell-stabilizing macromolecule, and of a natural halophyte (Salicornia fruticosa), yielded an enrichment factor (ε) of -2.00 ± 0.23‰ (1σ, n = 8) for pectin and -1.82 ± 0.02‰ (1σ, n = 4) for Salicornia (the relative amount of the heavier 81Br was decreased in CH3Br compared to the substrate salt). For short incubations, and up to 10% consumption of the salt substrate, this isotope effect was similar for temperatures from 30 up to 300 °C. For longer incubations of up to 90 h at 180 °C the δ81Br values increased from -2‰ to 0‰ for pectin and to -1‰ for Salicornia. These δ81Br source signatures of CH3Br formation from plant matter combine with similar data for carbon isotopes to facilitate multidimensional isotope diagnostics of the CH3Br budget.

  12. Bulk Sediment Hf-Nd Isotopic Composition Across the EOT, Northern Hemisphere Glaciation?

    NASA Astrophysics Data System (ADS)

    Duggan, B.; Buckley, W. P., Jr.; Bizimis, M.; Scher, H. D.

    2015-12-01

    In recent decades, near and far field proxies of continental ice production indicate the presence of continental ice on Antarctica. Short Antarctic glaciations blinked in and out of existence throughout the middle and late Eocene, culminating in the formation of a continental ice sheet during the Eocene Oligocene Transition (EOT; ~34 Ma). Moreover, the onset of the Antarctic glaciation coincides with pCO2 declining below a critical threshold for the accumulation of a continental ice sheet. New evidence suggesting bipolar glaciation (that is, northern and southern hemisphere) occurred through this period with ice sheets on Greenland and Antarctica. However, the pCO2 threshold for the accumulation of ice on Greenland is not reached until the late Oligocene. Preliminary hafnium-neodymium (Hf-Nd) isotope results of oxyhydroxide leachates from IODP Site U1411 on the Newfoundland Ridge points to increased weathering intensity coinciding with the EOT, marked by less radiogenic Hf isotope compositions. One interpretation of this data is that glaciation of the northern hemisphere (e.g. Greenland) coincides with that of Antarctica during the EOT. Hf-Nd isotopic composition of sediment on the Newfoundland ridge indicates a shift from incongruous chemical weathering to a more congruous mechanical weathering regime (i.e. glaciers). However, it could be suggested that the observed congruous Hf-Nd isotopic signal originates in the southern ocean and has been propagated north from the Antarctic. We are using sediment core from the equatorial Pacific to determine if a signal of glacial weathering could be transmitted though deep waters from Antarctica. The core, IODP Site 1333, is in the equatorial Pacific positioned far from either pole thus, a shift towards a less radiogenic Hf isotopic compositions is not to be expected. The absence of a shift in Hf isotopes in the oxydroxide leachates, or a shift of lesser magnitude, will strengthen the possibility of northern hemisphere

  13. Atmosphere-surface water exchanges from measurements of isotopic composition at a tall tower in Boulder

    NASA Astrophysics Data System (ADS)

    Noone, D. C.; Risi, C.; Raudzens Bailey, A.; Brown, D. P.; Buenning, N. H.; Gregory, S. A.; Nusbaumer, J.; Sykes, J.; Schneider, D. P.; Vanderwende, B. J.; Wong, J.; Wolfe, D. E.

    2010-12-01

    The exchange of water and carbon between the atmosphere and land remains poorly understood, particularly in regions of complex terrain and in the case of stable nighttime boundary layers. Profile measurements of the isotopic composition of water vapor were made at the 300 meter NOAA Boulder Atmospheric Observatory tall tower facility in Erie in February of 2010 to establish how well moisture budgets can be constrained with isotopic information. Measurements were made by placing instruments on the tower elevator and manually controlling the ascent and decent every 15 minutes for a total of 311 profiles. The four-day experiment followed a snow storm that produced 25-50 mm of snow. Temporal variations in the measured isotopic composition are dominated by the synoptic meteorology rather than local processes. Although both the “Keeling plot” approach applied to time series and the mixing lines applied to vertical profiles emerge algebraically from simple turbulence theory, only the latter is successful in estimating end members in good agreement with the known isotopic composition of the source water. However, mixing lines are only formed when conditions are stationary, and the approach generally fails during times of changes in the profile associated with regional advection. Rapid ventilation of the boundary layer during the day is found from the isotopic data because evaporation of the snow melt tags the gas transport. Weak transport at night is determined using CO2 profiles because respiration contrasts with the tropospheric baseline. We find that transport at night is characterized by slow mixing interrupted by fast mixing events. The intermittent exchange appears important for the net exchange and it is not clear that they are captured in turbulence schemes in climate models. Because the mixing line method is not uniformly successful, our results suggest a more complete framework based on boundary layer dynamics is needed for isotopic profiles to be meaningful.

  14. Mineralogy and Oxygen Isotope Compositions of Two C-Rich Hydrated Interplanetary Dust Particles

    NASA Technical Reports Server (NTRS)

    Snead, C. J.; McKeegan, K. D.; Messenger, S.; Nakamura-Messenger, K.

    2012-01-01

    Oxygen isotopic compositions of chondrites reflect mixing between a O-16-rich reservoir and a O-17,O-18-rich reservoir produced via mass-independent fractionation. The composition of the O-16-rich reservoir is reasonably well constrained, but material representing the O-17,O-18-rich end-member is rare. Self-shielding models predict that cometary water, presumed to represent this reservoir, should be enriched in O-17 and O-18 18O by > 200%. Hydrated interplanetary dust particles (IDPs) rich in carbonaceous matter may be derived from comets; such particles likely contain the products of reaction between O-16-poor water and anhydrous silicates that formed in the inner solar system. Here we present mineralogy and oxygen isotope compositions of two C-rich hydrated IDPs, L2083E47 and L2071E35.

  15. Hydrogeochemical and Isotopic Composition of Pasinler Geothermal Water (Erzurum, Turkey)

    NASA Astrophysics Data System (ADS)

    Hatipoglu, E.; Sunnetci, M. O.; Gultekin, F.

    2013-12-01

    In this investigation Pasinler (Erzurum) hot water spring has been studied from the point of geology and environmental isotopes. The Pasinler geothermal field is located 37 km east of Erzurum Province. The basement of Pasinler Geothermal field consists of Upper Cretaceous ophiolitic melange, shale, claystone, marl, and limestones, Eocene gabbro, andesite, basalt, trachyandesite, Oligocene andesite and basalt, Lower Miocene reef limestones, Upper Miocene pyroclastics, Plio- Quaternary (sandstone, marl, conglomerate) and Quaternary alluvium. The rhyolite is the reservoir for the geothermal fluid. The tuffs and marls are cap rocks of the system. The fault and related fractures around the Pasinler geothermal field provide pathways for the upward flow of geothermal fluid to the surface. The Alluvium around the Hasankale River is the most important unit as cold groundwater deposits in the study area. The thermal waters in the Pasinler geothermal fields have outlet temperatures of 23 to 35°C in springs. But discharge temperatures in the wells vary between 38-52°C. Geothermal well waters belong to the Na-Ca-Cl-HCO3 type. The Pasinler geothermal water has discharge pH values of 6 to 6.6, electrical conductivity (EC) of 970 to 6233 μS/cm, and TDS values between 635 and 4304 mg/l. δ18O, δ2H and δ3H isotope analyses were carried out to determine the origin of waters, recharge altitude, precipitation types, and groundwater circulation. In the 18O-δ 2H diagram all of the waters in the study area situated near the Globol Meteoric Water Line (GMWL) and indicate meteoric origin with little to no evaporation. According to the δ18O - temperature relation all water samples recharged at the same elevation in the plain. Low tritium coupled with high electrical conductivity and high Cl-value in the Pasinler thermal spring indicate that this spring has deep circulation. In order to determinate the origin of sulphure (SO4) and carbon in the waters, all waters were analysed for

  16. A non-terrestrial 16O-rich isotopic composition for the protosolar nebula.

    PubMed

    Hashizume, Ko; Chaussidon, Marc

    2005-03-31

    The discovery in primitive components of meteorites of large oxygen isotopic variations that could not be attributed to mass-dependent fractionation effects has raised a fundamental question: what is the composition of the protosolar gas from which the host grains formed? This composition is probably preserved in the outer layers of the Sun, but the resolution of astronomical spectroscopic measurements is still too poor to be useful for comparison with planetary material. Here we report a precise determination of the oxygen isotopic composition of the solar wind from particles implanted in the outer hundreds of nanometres of metallic grains in the lunar regolith. These layers of the grains are enriched in 16O by >20 +/- 4 per thousand relative to the Earth, Mars and bulk meteorites, which implies the existence in the solar accretion disk of reactions--as yet unknown--that were able to change the 17O/16O and 18O/16O ratios in a way that was not dependent strictly on the mass of the isotope. Photochemical self-shielding of the CO gas irradiated by ultraviolet light may be one of these key processes, because it depends on the abundance of the isotopes, rather than their masses. PMID:15800617

  17. The isotopic composition of methane in the stratosphere: high-altitude balloon sample measurements

    NASA Astrophysics Data System (ADS)

    Röckmann, T.; Brass, M.; Borchers, R.; Engel, A.

    2011-04-01

    The isotopic composition of stratospheric methane has been determined on a large suite of air samples from stratospheric balloon flights covering subtropical to polar latitudes and a time period of 16 yr. 154 samples were analyzed for δisotope fractionation processes accordingly increase the isotopic composition up to δ13C=-14‰ and δD= +190‰, the largest enrichments observed for atmospheric CH4 so far. When analyzing and comparing kinetic isotope effects (KIEs) derived from single balloon profiles, it is necessary to take into account the residence time in the stratosphere in combination with the observed mixing ratio and isotope trends in the troposphere, and the range of isotope values covered by the individual profile. Temporal isotope trends can also be determined in the stratosphere and compare reasonably well with the tropospheric trends. The effects of chemical and dynamical processes on the isotopic composition of CH4 in the stratosphere are discussed in detail. Different ways to interpret the data in terms of the relative fractions of the three important sink mechanisms (reaction with OH, O(1D)) and Cl, respectively), and their limitations, are investigated. The classical approach of using global mean KIE values can be strongly biased when profiles with different minimum mixing ratios are compared. Approaches for more local KIE investigations are suggested. It is shown that any approach for a formal sink partitioning from the measured data severely underestimates the fraction removed by OH, which is likely due to the insensitivity of the measurements to the kinetic fractionation in the

  18. Potassium isotopic compositions of NIST potassium standards and 40Ar/39Ar mineral standards

    NASA Astrophysics Data System (ADS)

    Morgan, L. E.; Tappa, M.; Ellam, R. M.; Mark, D. F.; Lloyd, N. S.; Higgins, J. A.; Simon, J. I.

    2013-12-01

    Knowledge of the isotopic ratios of standards, spikes, and reference materials is fundamental to the accuracy of many geochronological methods. For example, the 238U/235U ratio relevant to U-Pb geochronology was recently re-determined [1] and shown to differ significantly from the previously accepted value employed during age determinations. These underlying values are fundamental to accurate age calculations in many isotopic systems, and uncertainty in these values can represent a significant (and often unrecognized) portion of the uncertainty budget for determined ages. The potassium isotopic composition of mineral standards, or neutron flux monitors, is a critical, but often overlooked component in the calculation of K-Ar and 40Ar/39Ar ages. It is currently assumed that all terrestrial materials have abundances indistinguishable from that of NIST SRM 985 [2]; this is apparently a reasonable assumption at the 0.25‰ level (1σ) [3]. The 40Ar/39Ar method further relies on the assumption that standards and samples (including primary and secondary standards) have indistinguishable 40K/39K values. We will present data establishing the potassium isotopic compositions of NIST isotopic K SRM 985, elemental K SRM 999b, and 40Ar/39Ar biotite mineral standard GA1550 (sample MD-2). Stable isotopic compositions (41K/39K) were measured by the peak shoulder method with high resolution MC-ICP-MS (Thermo Scientific NEPTUNE Plus), using the accepted value of NIST isotopic SRM 985 [2] for fractionation [4] corrections [5]. 40K abundances were measured by TIMS (Thermo Scientific TRITON), using 41K/39K values from ICP-MS measurements (or, for SRM 985, values from [2]) for internal fractionation corrections. Collectively these data represent an important step towards a metrologically traceable calibration of 40K concentrations in primary 40Ar/39Ar mineral standards and improve uncertainties by ca. an order of magnitude in the potassium isotopic compositions of standards. [1] Hiess

  19. Lead Isotopic Composition and Trace Metals in Aerosols for Source Apportionment

    NASA Astrophysics Data System (ADS)

    Chien, C. T.; Paytan, A.

    2014-12-01

    Transported thousands of miles away from their source, aerosols can be dispersed and deposition throughout the Earth's surface. Aerosols from natural and industrial sources have different characteristics and health impacts thus it is important to identify their sources. The lead isotopic composition and trace metals in aerosol samples collected in different regions and periods around the world can help us better understand spatial and seasonal variation of aerosol sources. Aerosol samples collected in California, Bermuda, China and the Red Sea have been analyzed. The trace metal and Pb isotopes in these samples provide information regarding the various sources of aerosols to these sites.

  20. Preservation of Earth-forming events in the tungsten isotopic composition of modern flood basalts

    NASA Astrophysics Data System (ADS)

    Rizo, Hanika; Walker, Richard J.; Carlson, Richard W.; Horan, Mary F.; Mukhopadhyay, Sujoy; Manthos, Vicky; Francis, Don; Jackson, Matthew G.

    2016-05-01

    How much of Earth's compositional variation dates to processes that occurred during planet formation remains an unanswered question. High-precision tungsten isotopic data from rocks from two large igneous provinces, the North Atlantic Igneous Province and the Ontong Java Plateau, reveal preservation to the Phanerozoic of tungsten isotopic heterogeneities in the mantle. These heterogeneities, caused by the decay of hafnium-182 in mantle domains with high hafnium/tungsten ratios, were created during the first ~50 million years of solar system history, indicating that portions of the mantle that formed during Earth’s primary accretionary period have survived to the present.

  1. Preservation of Earth-forming events in the tungsten isotopic composition of modern flood basalts.

    PubMed

    Rizo, Hanika; Walker, Richard J; Carlson, Richard W; Horan, Mary F; Mukhopadhyay, Sujoy; Manthos, Vicky; Francis, Don; Jackson, Matthew G

    2016-05-13

    How much of Earth's compositional variation dates to processes that occurred during planet formation remains an unanswered question. High-precision tungsten isotopic data from rocks from two large igneous provinces, the North Atlantic Igneous Province and the Ontong Java Plateau, reveal preservation to the Phanerozoic of tungsten isotopic heterogeneities in the mantle. These heterogeneities, caused by the decay of hafnium-182 in mantle domains with high hafnium/tungsten ratios, were created during the first ~50 million years of solar system history, indicating that portions of the mantle that formed during Earth's primary accretionary period have survived to the present. PMID:27174983

  2. On the iron isotope composition of Mars and volatile depletion in the terrestrial planets

    NASA Astrophysics Data System (ADS)

    Sossi, Paolo A.; Nebel, Oliver; Anand, Mahesh; Poitrasson, Franck

    2016-09-01

    Iron is the most abundant multivalent element in planetary reservoirs, meaning its isotope composition (expressed as δ57Fe) may record signatures of processes that occurred during the formation and subsequent differentiation of the terrestrial planets. Chondritic meteorites, putative constituents of the planets and remnants of undifferentiated inner solar system bodies, have δ57Fe ≈ 0 ‰; an isotopic signature shared with the Martian Shergottite-Nakhlite-Chassignite (SNC) suite of meteorites. The silicate Earth and Moon, as represented by basaltic rocks, are distinctly heavier, δ57Fe ≈ + 0.1 ‰. However, some authors have recently argued, on the basis of iron isotope measurements of abyssal peridotites, that the composition of the Earth's mantle is δ57Fe = + 0.04 ± 0.04 ‰, indistinguishable from the mean Martian value. To provide a more robust estimate for Mars, we present new high-precision iron isotope data on 17 SNC meteorites and 5 mineral separates. We find that the iron isotope compositions of Martian meteorites reflect igneous processes, with nakhlites and evolved shergottites displaying heavier δ57Fe (+ 0.05 ± 0.03 ‰), whereas MgO-rich rocks are lighter (δ57Fe ≈ - 0.01 ± 0.02 ‰). These systematics are controlled by the fractionation of olivine and pyroxene, attested to by the lighter isotope composition of pyroxene compared to whole rock nakhlites. Extrapolation of the δ57Fe SNC liquid line of descent to a putative Martian mantle yields a δ57Fe value lighter than its terrestrial counterpart, but indistinguishable from chondrites. Iron isotopes in planetary basalts of the inner solar system correlate positively with Fe/Mn and silicon isotopes. While Mars and IV-Vesta are undepleted in iron and accordingly have chondritic δ57Fe, the Earth experienced volatile depletion at low (1300 K) temperatures, likely at an early stage in the solar nebula, whereas additional post-nebular Fe loss is possible for the Moon and angrites.

  3. Southern Greenland water vapour isotopic composition at the crossroads of Atlantic and Arctic moisture

    NASA Astrophysics Data System (ADS)

    Bonne, J. L.; Steen-Larsen, H. C.; Risi, C. M.; Werner, M.; Sodemann, H.; Lacour, J. L.; Fettweis, X.; Cesana, G.; Delmotte, M.; Cattani, O.; Clerbaux, C.; Sveinbjörnsdottir, A. E.; Masson-Delmotte, V.

    2014-12-01

    Since September 2011, a continuous water vapour isotopic composition monitoring instrument has been remotely operated in Ivittuut (61.21°N, 48.17°W), southern Greenland. Meteorological parameters are monitored and precipitation has been sampled and analysed for isotopic composition, suggesting equilibrium between surface vapour and precipitation. The data depict small summer diurnal variations. δ18O and deuterium excess (d-excess) are generally anti-correlated and show important seasonal variations (with respective amplitudes of 10 and 20 ‰), and large synoptic variations associated to low-pressure systems (typically +5‰ on δ18O and -15‰ on d-excess). The moisture sources, estimated based on Lagrangian back-trajectories, are primarily influenced by the western North Atlantic, and north-eastern American continent. Notable are important seasonal and synoptic shifts of the moisture sources, and sporadic influences of the Arctic or the eastern North Atlantic. Moisture sources variations can be related to changes in water vapour isotopic composition, and the isotopic fingerprints can be attributed to the areas of moisture origins. Isotopic enabled AGCMs nudged to meteorology (LMDZiso, ECHAM5-wiso), despite biases, correctly capture the δ18O changes, but underestimate the d-excess changes. They allow to identify a high correlation between the southern Greenland d-excess and the simulated relative humidity and d-excess in the moisture source region south of Greenland. An extreme high temperature event in July 2012 affecting all Greenland, similar to ice sheet melt events during the medieval periods and one event in 1889 documented by Greenland ice core records, has been analysed regarding water vapour isotopic composition, using remote sensing (IASI) and in situ observations from Bermuda to northern Greenland (NEEM station). Our southern Greenland observations allow to track the water vapour evolution during this event along the moisture transport path

  4. The Oxygen Isotopic Composition of MIL 090001: A CR2 Chondrite with Abundant Refractory Inclusions

    NASA Technical Reports Server (NTRS)

    Keller, Lindsay P.; McKeegan, K. D.; Sharp, Z. D.

    2012-01-01

    MIL 090001 is a large (>6 kg) carbonaceous chondrite that was classified as a member of the CV reduced subgroup (CVred) that was recovered during the 2009-2010 ANSMET field season [1]. Based on the abundance of refractory inclusions and the extent of aqueous alteration, Keller [2] suggested a CV2 classification. Here we report additional mineralogical and petrographic data for MIL 090001, its whole-rock oxygen isotopic composition and ion microprobe analyses of individual phases. The whole rock oxygen isotopic analyses show that MIL 090001 should be classified as a CR chondrite.

  5. Isotopic Composition of Gaseous Elemental Mercury (Hg0) at Various Sites in Japan

    NASA Astrophysics Data System (ADS)

    Yamakawa, A.; Moriya, K.; Yoshinaga, J.

    2015-12-01

    Mercury (Hg) is a toxic heavy metal, which exists in various chemical forms in the environmental system. In the atmosphere, Hg exists in three forms (Hg0(g), Hg+2(g), and Hg(p)). Hg0(g) is the dominant species of atmospheric Hg, accounting for >95% of the total Hg in the atmosphere. Because Hg0(g) is highly volatile and has limited solubility in water, it cannot be easily removed by wet or dry deposition processes. Therefore, the residence time of Hg0(g) in the atmosphere is relatively long (1 to 2 years), allowing long-range transport from mercury emission source(s). Conversely, Hg+2(g) and Hg(p) are effectively removed from the atmosphere through wet and dry depositions. The determination of mercury source attribution using quantitative data is challenging because Hg0(g) may be deposited on an area upon oxidation to Hg+2(g) and associated with aerosols and particulates to form Hg(p) while the global cycling of Hg0(g). Over the last decade, the development of analytical methods of highly precise Hg isotopic measurements demonstrated mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) of Hg isotopes in environmental samples. For instance, MDF of Hg isotopes is thought to occur during various natural and industrial Hg transformations. MIF of Hg isotopes is observed during abiotic reduction, photochemical and non-photochemical, and physical and chemical processes. Such processes lead to differences in the Hg isotopic composition of different emission sources, both natural and anthropogenic, and atmospheric processes (i.e., transportation, oxidation/reduction, deposition, and reemission). Therefore, Hg isotopic compositions could be used to trace the sources and processes of atmospheric Hg. For securing the reliability and accuracy of atmospheric Hg isotope data, the methods of collection, pretreatment, and isotopic measurement for Hg0(g) were developed to obtain high recovery yield of samples with no Hg isotopic fractionation during each

  6. Regulation of Isotopic Composition of Water - way of Improvement of Cosmonauts Drinking Water Functional Properties

    NASA Astrophysics Data System (ADS)

    Kulikova, Ekaterina; Utina, Dina; Vorozhtsova, Svetlana; Severyuhin, Yuri; Abrosimova, Anna; Sinyak, Yuri; Ivanov, Alexander

    The problem in providing drinking water to cosmonauts is solved - at this moment there is a task to improve the functional properties of the water. One of the perspectives of this trend is the use of light isotopic water. The animal studies have shown that long-term consumption of water with a depletion of deuterium and oxygen heavy isotopes accelerates the rise of mass non-irradiated mice, the phase fluctuations reducing or increasing hematological parameters were having adaptive nature. These fluctuations didn’t overcome values beyond the physiological norm of this type of animal. It is established that the therapeutic use of light isotopic water with 35 - 90 ppm in deuterium increases the survival of irradiated mice by an average of 30%, contributes to the preservation of irradiated animals body weight. Treatment of acute radiation sickness with light isotopic water stimulates hematopoietic recovery. At the same time, keeping mice drinking light isotopic water for 7 - 8 days before the irradiation (from 4 to 8.5 Gr) has no effect on the level of radio resistance. Longer keeping mice on light isotopic water, for 14 -21 days - reduction in life expectancy, animal mass, bone marrow cellularity and the level of white blood cells in irradiated animals is noted. It was established that keeping mice on light isotopic water for 14 days before exposure in experimental animals causes an increase in the mitotic index and the frequency of formation of aberrant mitosis after 24 hours of Co(60) gamma radiation in doses of 1 , 2, and 4 Gr. Thus, it is clear that the regulation of the isotopic composition of drinking water - way to improve its functional properties.

  7. Carbon Isotopic Composition Of Earlydiagenetic Methane: Variations With Sediments Depth

    NASA Astrophysics Data System (ADS)

    Jędrysek, Mariusz Orion; Hałas, Stanisław; Pieńkos, Tomasz

    2015-03-01

    We demonstrate the annual cycle of methane in fresh sediments of two lakes - Moszne (E Poland) and Skrzynka (W Poland). The vertical gradient in δ13C(CH4) values varied widely from about -4.5‰/(-1 m) in late summer 1993 to about +2.5‰/(-1 m) in late winter, in the uppermost sediment profiles of about 3-meters in length. These vertical variations apparently are not due to oxidation or temperature changes, but rather to the higher gradient of the downward decrease of production rates via the acetic acid fermen-tation pathway rather than via the CO2-H2 pathway. The production of methane and δ13C(CH4) values are the highest during summer while the lowest during winter, reflect-ed especially during surface sampling. The downward gradient of δ13C in winter, late autumn and, at greater depths, in late summer results from isotope enrichment of the residual pool of precursors of methane, predominantly CO2.

  8. Constraints on Phanerozoic paleotemperature and seawater oxygen isotope evolution from the carbonate clumped isotope compositions of Late Paleozoic marine fossils (Invited)

    NASA Astrophysics Data System (ADS)

    Henkes, G. A.; Passey, B. H.; Grossman, E. L.; Pérez-Huerta, A.; Shenton, B.; Yancey, T. E.

    2013-12-01

    A long-standing geoscience controversy has been the interpretation of the observed several per mil increase in the oxygen isotope compositions of marine calcites over the Phanerozoic Eon. Explanations for this trend have included decreasing seawater paleotemperatures, increasing seawater oxygen isotope values, and post-depositional calcite alteration. Carbonate clumped isotope paleothermometry is a useful geochemical tool to test these hypotheses because of its lack of dependence on the bulk isotopic composition of the water from which carbonate precipitated. This technique is increasingly applied to ancient marine invertebrate shells, which can be screened for diagenesis using chemical and microstructural approaches. After several years of clumped isotope analysis of these marine carbonates in a handful of laboratories, a long-term temperature and isotopic trend is emerging, with the results pointing to relatively invariant seawater δ18O and generally decreasing seawater temperatures through the Phanerozoic. Uncertainties remain, however, including the effects of reordering of primary clumped isotope compositions via solid-state diffusion of C and O through the mineral lattice at elevated burial temperatures over hundred million year timescales. To develop a quantitative understanding of such reordering, we present data from laboratory heating experiments of late Paleozoic brachiopod calcite. When combined with kinetic models of the reordering reaction, the results of these experiments suggest that burial temperatures less than ~120 °C allow for preservation of primary brachiopod clumped isotope compositions over geological timescales. Analyses of well-preserved Carboniferous and Permian brachiopods reinforce these results by showing that shells with apparent clumped isotope temperatures of ~150 °C are associated with deep sedimentary burial (>5 km), whereas those with putatively primary paleotemperatures in the 10-30 °C range experienced no more than ~1.5 km

  9. Isotope Compositions of Submarine North Kona Tholeiitic Lavas, Hualalai Volcano, Hawaii

    NASA Astrophysics Data System (ADS)

    Yamasaki, S.; Tagami, T.; Kani, T.; Hanan, B. B.

    2006-12-01

    Four remote and manned submersible dives examined the deep submarine portion of the North Kona region, offshore Hualalai during 2001 and 2002 JAMSTEC cruises. The dives encountered compositionally homogeneous tholeiitic pillow lavas that are interpreted to have erupted from Hualalai during its shield stage. Hualalai volcano, the westernmost volcano on the Island of Hawaii is presently in the post-shield alkalic stage and most of its subaerial surface is covered by alkalic basalt. Difficulty accessing buried tholeiite is one reason that compositional data from the volumetrically dominant stage in the volcano's edifice are scarce. To identify source materials involved in shield stage of Hualalai can provide important information about the isotopic variation and evolution during Hawaiian volcano growth. We report the results of Hf, Pb, Sr, Nd isotopic compositions of 34 tholeiitic lava samples collected from submarine North Kona region. Hf, Nd, Sr isotopic compositions of the submarine North Kona lavas are similar to Mauna Loa tholeiites, and define a clear mixing line showing that the mantle source consists of at least two components. Some of new Pb isotopic data have higher 207Pb/204Pb and ^{208}Pb/204Pb, for a given 206Pb/204Pb, than published data from Mauna Loa and Hualalai. The trend emerges towards to 'Kea'-like component. Although in general Hawaiian basalts require more than two components to account for their geochemical variations, the isotopic variations in Hualalai shield lavas appear dominated by a mixture of two components: 'Koolau'-like enriched component and a 'Kea'-like depleted component, and contributed to relatively higher proportion of the 'Kea'-like component than the Mauna Loa.

  10. Stable isotope composition of waters in the Great Basin, United States 1. Air-mass trajectories

    USGS Publications Warehouse

    Friedman, I.; Harris, J.M.; Smith, G.I.; Johnson, C.A.

    2002-01-01

    Isentropic trajectories, calculated using the NOAA/Climate Monitoring and Diagnostics Laboratory's isentropic transport model, were used to determine air-parcel origins and the influence of air mass trajectories on the isotopic composition of precipitation events that occurred between October 1991 and September 1993 at Cedar City, Utah, and Winnemucca, Nevada. Examination of trajectories that trace the position of air parcels backward in time for 10 days indicated five distinct regions of water vapor origin: (1) Gulf of Alaska and North Pacific, (2) central Pacific, (3) tropical Pacific, (4) Gulf of Mexico, and (5) continental land mass. Deuterium (??D) and oxygen-18 (??18O) analyses were made of precipitation representing 99% of all Cedar City events. Similar analyses were made on precipitation representing 66% of the precipitation falling at Winnemucca during the same period. The average isotopic composition of precipitation derived from each water vapor source was determined. More than half of the precipitation that fell at both sites during the study period originated in the tropical Pacific and traveled northeast to the Great Basin; only a small proportion traversed the Sierra Nevada. The isotopic composition of precipitation is determined by air-mass origin and its track to the collection station, mechanism of droplet formation, reequilibration within clouds, and evaporation during its passage from cloud to ground. The Rayleigh distillation model can explain the changes in isotopic composition of precipitation as an air mass is cooled pseudo-adiabatically during uplift. However, the complicated processes that take place in the rapidly convecting environment of cumulonimbus and other clouds that are common in the Great Basin, especially in summer, require modification of this model because raindrops that form in the lower portion of those clouds undergo isotopic change as they are elevated to upper levels of the clouds from where they eventually drop to the

  11. Stable isotope composition of waters in the Great Basin, United States 1. Air-mass trajectories

    NASA Astrophysics Data System (ADS)

    Friedman, Irving; Harris, Joyce M.; Smith, George I.; Johnson, Craig A.

    2002-10-01

    Isentropic trajectories, calculated using the NOAA/Climate Monitoring and Diagnostics Laboratory's isentropic transport model, were used to determine air-parcel origins and the influence of air mass trajectories on the isotopic composition of precipitation events that occurred between October 1991 and September 1993 at Cedar City, Utah, and Winnemucca, Nevada. Examination of trajectories that trace the position of air parcels backward in time for 10 days indicated five distinct regions of water vapor origin: (1) Gulf of Alaska and North Pacific, (2) central Pacific, (3) tropical Pacific, (4) Gulf of Mexico, and (5) continental land mass. Deuterium (δD) and oxygen-18 (δ18O) analyses were made of precipitation representing 99% of all Cedar City events. Similar analyses were made on precipitation representing 66% of the precipitation falling at Winnemucca during the same period. The average isotopic composition of precipitation derived from each water vapor source was determined. More than half of the precipitation that fell at both sites during the study period originated in the tropical Pacific and traveled northeast to the Great Basin; only a small proportion traversed the Sierra Nevada. The isotopic composition of precipitation is determined by air-mass origin and its track to the collection station, mechanism of droplet formation, reequilibration within clouds, and evaporation during its passage from cloud to ground. The Rayleigh distillation model can explain the changes in isotopic composition of precipitation as an air mass is cooled pseudo-adiabatically during uplift. However, the complicated processes that take place in the rapidly convecting environment of cumulonimbus and other clouds that are common in the Great Basin, especially in summer, require modification of this model because raindrops that form in the lower portion of those clouds undergo isotopic change as they are elevated to upper levels of the clouds from where they eventually drop to the

  12. Mapping Precipitation Patterns from the Stable Isotopic Composition of Surface Waters: Olympic Peninsula, Washington State

    NASA Astrophysics Data System (ADS)

    Anders, A. M.; Brandon, M. T.

    2008-12-01

    Available data indicate that large and persistent precipitation gradients are tied to topography at scales down to a few kilometers, but precipitation patterns in the majority of mountain ranges are poorly constrained at scales less than tens of kilometers. A lack of knowledge of precipitation patterns hampers efforts to understand the processes of orographic precipitation and identify the relationships between geomorphic evolution and climate. A new method for mapping precipitation using the stable isotopic composition of surface waters is tested in the Olympic Mountains of Washington State. Measured δD and δ18O of 97 samples of surface water are linearly related and nearly inseparable from the global meteoric water line. A linear orographic precipitation model extended to include in effects of isotopic fractionation via Rayleigh distillation predicts precipitation patterns and isotopic composition of surface water. Seven parameters relating to the climate and isotopic composition of source water are used. A constrained random search identifies the best-fitting parameter set. Confidence intervals for parameter values are defined and precipitation patterns are determined. Average errors for the best-fitting model are 4.8 permil in δD. The difference between the best fitting model and other models within the 95% confidence interval was less than 20%. An independent high-resolution precipitation climatology documents precipitation gradients similar in shape and magnitude to the model derived from surface water isotopic composition. This technique could be extended to other mountain ranges, providing an economical and fast assessment of precipitation patterns requiring minimal field work.

  13. The origin of decoupled Hf-Nd isotope compositions in Eoarchean rocks from southern West Greenland

    NASA Astrophysics Data System (ADS)

    Hoffmann, J. Elis; Münker, Carsten; Polat, Ali; Rosing, Minik T.; Schulz, Toni

    2011-11-01

    Radiogenic isotope compositions of Hf and Nd are typically coupled in Phanerozoic and Proterozoic mafic rocks due to a similar behaviour of Lu-Hf and Sm-Nd during mantle melting. Eoarchean rocks, for instance those from southern West Greenland, exhibit an apparent decoupling of Hf and Nd isotope compositions. This apparent decoupling may either indicate metamorphic disturbance or, alternatively, mirror early differentiation processes in the silicate Earth. To evaluate the issue, we performed combined measurements of Hf-Nd isotope compositions together with major and trace element concentrations for well preserved >3720 to >3800 Ma old tholeiitic metabasalts and gabbros from the ˜3700 Ma and ˜3800 Ma old terranes of the Isua Supracrustal Belt, southern West Greenland. In contrast to younger mafic rocks, calculated initial ɛHf-ɛNd values of the Isua tholeiites show similar spreads and are both near chondritic to strongly depleted (-0.7 to +6.3 and -0.8 to +4.4, respectively), also in contrast to previously reported more depleted signatures in nearby boninite-like metabasalts of the Garbenschiefer unit. An evaluation of alteration effects based on preserved major and trace element arrays reveals pristine magmatic trends and therefore the measured isotope compositions indeed in most cases characterize contrasting Eoarchean mantle sources. In accord with this view, compositions of the Isua metabasalts yield Eoarchean regression ages in Sm-Nd and Lu-Hf isochron spaces, overlapping with emplacement ages inferred from crosscutting relationships with tonalites. Lutetium-Hf systematics of the Isua metabasalts studied here, yield clear isochron relationships. For both terranes, there is some scatter in Sm-Nd space, indicating early disturbance of the Sm-Nd system close in time to the extrusion ages, possibly by seafloor alteration. Trace element compositions of the metabasalts indicate an arc setting and a strong source overprint by melt-like subduction components. It is

  14. Modeling Environmental Controls on the Carbon Isotope Composition of Ecosystem Respired Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Cai, T.; Flanagan, L. B.

    2006-12-01

    Our main objective was to test whether the carbon isotope composition of ecosystem respired CO2 varied in response to environmental conditions in a manner consistent with well-known leaf-level studies of photosynthetic 13C discrimination. We developed an ecosystem-scale model that calculated leaf CO2 assimilation, stomatal conductance and chloroplast CO2 concentration separately for sunlit and shaded leaves within multiple canopy layers. The stomatal conductance model was linked to differences in water potential and resistances in the hydraulic pathway between the soil and the tree foliage. This part of the ecosystem model was validated by comparison to leaf-level gas exchange measurements and estimates of ecosystem-scale photosynthesis (GEP). The estimates of GEP were based on eddy covariance measurements of net ecosystem CO2 exchange (NEE) and the Fluxnet-Canada Research Network standard protocol for partitioning NEE into GEP and total ecosystem respiration (TER). The carbon isotope composition of carbohydrate formed during photosynthesis was calculated based on the Farquhar model of isotope effects. Total ecosystem respiration was modeled, based on measured temperature and soil moisture, as the sum of four components (1) above-ground plant, (2) root, (3) litter, and (4) mineral soil. We applied a variety of techniques to allocate the contribution of these different components so that modeled TER was consistent with TER calculated from NEE measurements. The carbon isotope composition of CO2 released during above-ground plant and root respiration was calculated based on an assimilated-weighted average of carbohydrate fixed during a variable number of days previous to the day of respiration. The isotope composition of CO2 released by litter and mineral soil respiration was based on measurements of the δ13C values of these components (we assumed no isotope fractionation during respiration) and held constant in all calculations. The model was compared to

  15. Predicting the Isotopic Composition of Subduction-Filtered Subducted Oceanic Crust and Sediment

    NASA Astrophysics Data System (ADS)

    White, W. M.

    2010-12-01

    The chemical and isotopic character of mantle plumes, which produce oceanic island volcanoes, are widely thought to reflect the presence of recycled oceanic crust and sediment. Isotopic systematics suggest the “cycle time” for this process is 1 Ga or longer, but it should be possible to use a simple mass balance approach to discern how the presently operating subduction zone filter affects the ratios of radioactive parent to radiogenic daughter isotopes. Simple uniformitarian assumptions can then be used to predict the present isotopic composition of anciently subducted lithosphere. Our underlying assumption in deciphering the subduction zone filter is that the flux of an element into the deep mantle is simply equal to the flux of element into the subduction zone less the flux of that element into subduction zone magmas. The former is readily calculated from published data. The latter can be calculated by estimating parental magma compositions, arc accretion rates, and the assumption that arc magma compositions differ from MORB only because of material derived from subducting crust and sediment. Using this approach for 8 intra-oceanic subduction zones, we find 73% of Th and Pb, 79% of U, 80% of Rb and Sr, 93% of Nd and 98% of Sm survive the subduction zone filter. The subduction zone filter systematically increases Sm/Nd ratios in all subduction zones, but the effect is small, with a weighted mean increase of 1.5%. The effect of subduction is to decrease the Sm/Nd of the mantle, but only slightly. The effect of subduction is to increase the Rb/Sr of the mantle, but the subduction zone filter does not have a systematic effect on Rb/Sr ratios: it significantly increases in Rb/Sr in 3 subduction zones and significantly decreases it in one; the weighted mean shows no significant change. The effect of the subduction zone filter on U/Pb is also not systematic. U/Pb ratios in the mantle fluxes are bimodal, with values equal to or lower than the bulk Earth value in 4

  16. Absolute Summ

    NASA Astrophysics Data System (ADS)

    Phillips, Alfred, Jr.

    Summ means the entirety of the multiverse. It seems clear, from the inflation theories of A. Guth and others, that the creation of many universes is plausible. We argue that Absolute cosmological ideas, not unlike those of I. Newton, may be consistent with dynamic multiverse creations. As suggested in W. Heisenberg's uncertainty principle, and with the Anthropic Principle defended by S. Hawking, et al., human consciousness, buttressed by findings of neuroscience, may have to be considered in our models. Predictability, as A. Einstein realized with Invariants and General Relativity, may be required for new ideas to be part of physics. We present here a two postulate model geared to an Absolute Summ. The seedbed of this work is part of Akhnaton's philosophy (see S. Freud, Moses and Monotheism). Most important, however, is that the structure of human consciousness, manifest in Kenya's Rift Valley 200,000 years ago as Homo sapiens, who were the culmination of the six million year co-creation process of Hominins and Nature in Africa, allows us to do the physics that we do. .

  17. Chemical and sulfur isotopic composition of precipitation in Beijing, China.

    PubMed

    Zhu, Guangxu; Guo, Qingjun; Chen, Tongbin; Lang, Yunchao; Peters, Marc; Tian, Liyan; Zhang, Hanzhi; Wang, Chunyu

    2016-03-01

    China is experiencing serious acid rain contamination, with Beijing among the worst-hit areas. To understand the chemical feature and the origin of inorganic ions in precipitation of Beijing, 128 precipitation samples were collected and analyzed for major water-soluble ions and δ(34)S. The pH values ranged from 3.68 to 7.81 and showed a volume weighted average value (VWA) of 5.02, with a frequency of acid rain of 26.8 %. The VWA value of electrical conductivity (EC) was 68.6 μS/cm, which was nearly 4 times higher than the background value of northern China. Ca(2+) represented the main cation; SO4 (2-) and NO3 (-) were the dominant anion in precipitation. Our study showed that SO4 (2-) and NO3 (-) originated from coal and fossil fuel combustion; Ca(2+), Mg(2+), and K(+) were from the continental sources. The δ(34)S value of SO4 (2-) in precipitation ranged from +2.1 to +12.8‰ with an average value of +4.7‰. The δ(34)S value showed a winter maximum and a summer minimum tendency, which was mainly associated with temperature-dependent isotope equilibrium fractionation as well as combustion of coal with relatively positive δ(34)S values in winter. Moreover, the δ(34)S values revealed that atmospheric sulfur in Beijing are mainly correlated to coal burning and traffic emission; coal combustion constituted a significant fraction of the SO4 (2-) in winter precipitation. PMID:26573310

  18. The Influence of Temperature, pH, and Growth Rate on the Stable Isotope Composition of Calcite

    NASA Astrophysics Data System (ADS)

    Watkins, J. M.; Hunt, J. D.; Ryerson, F. J.; DePaolo, D. J.

    2014-12-01

    The oxygen isotope composition of carbonate minerals varies with temperature as well as other environmental variables. For carbonates that precipitate slowly, under conditions that approach thermodynamic equilibrium, the temperature-dependence of 18O uptake is the dominant signal and the measured 18O content can be used as a paleotemperature proxy. In the more common case where carbonate minerals grow in a regime where they are not in isotopic equilibrium with their host solution, their stable isotope compositions are a convolution of the effects of multiple environmental variables. We present results from inorganic calcite growth experiments demonstrating the occurrence of non-equilibrium oxygen isotope effects that vary systematically with pH and crystal growth rate. We have developed an isotopic ion-by-ion crystal growth model that quantifies the competing roles of temperature, pH, and growth rate, and provides a general description of calcite-water oxygen isotope fractionation under non-equilibrium conditions. The model predicts that (1) there are both equilibrium and kinetic contributions to calcite oxygen isotopes at biogenic growth rates, (2) calcite does not inherit the stable isotopic composition of dissolved inorganic carbon (DIC), (3) for oxygen isotopes there is a kinetically controlled variation of about 1‰ per pH unit between pH=7.7 and 9.3 at constant growth rate for inorganic calcite as well as the foraminifera Orbulina universa, and (4) extreme light isotope enrichments in calcite in alkaline environments are likely due to disequilibrium among DIC species in aqueous solution. The experimental and modeling approaches can be extended to carbon isotope as well as clumped isotope uptake into calcite but additional data are needed to constrain the kinetic fractionation factors for carbon isotopes and doubly-substituted isotopologues. The results will be discussed in the context of separating the relative influence of inorganic and biologic processes

  19. Isotopic composition of strontium in volcanic rocks from oahu.

    PubMed

    Powell, J L; Delong, S E

    1966-09-01

    Analysis of several well-documented specimens from each of the three volcanic series on Oahu gives the following mean ratios of Sr(87) to Sr(86): the Waianae series, 0.7030 +/- 0.00010 (sigma); the Koolau series, 0.70385+/- 0.00009 (sigma); and the Honolulu series, 0.7029 ++/- 0.00006 ( sigma). The mean ratio of Sr(87) to Sr(86) of the Koolau series specimens is significantly higher than the means of the other two series. With one exception, significant differences in Sr(87)/ Sr(86) within a series were not found, even though some large compositional differences existed. PMID:17754246

  20. Experimental assessment of environmental influences on the stable isotopic composition of Daphnia pulicaria and their ephippia

    NASA Astrophysics Data System (ADS)

    Schilder, J.; Tellenbach, C.; Möst, M.; Spaak, P.; van Hardenbroek, M.; Wooller, M. J.; Heiri, O.

    2015-02-01

    The stable isotopic composition of fossil resting eggs (ephippia) of Daphnia spp. is being used to reconstruct past environmental conditions in lake ecosystems. However, the underlying assumption that the stable isotopic composition of the ephippia reflects the stable isotopic composition of the parent Daphnia, of their diet and of the environmental water have yet to be confirmed in a controlled experimental setting. We performed experiments with Daphnia pulicaria cultures, which included a control treatment conducted at 12 °C in filtered lake water and with a diet of fresh algae, and three treatments in which we manipulated the stable carbon isotopic composition (δ13C value) of the algae, stable oxygen isotopic composition (δ18O value) of the water, and the water temperature, respectively. The stable nitrogen isotopic composition (δ15N value) of the algae was similar for all treatments. At 12 °C, differences in algal δ13C values and in δ18O values of water are reflected in those of Daphnia. The differences between ephippia and Daphnia stable isotope ratios were similar in the different treatments (δ13C: + 0.2 ± 0.4‰ (SD); δ15N: -1.6 ± 0.4‰; δ18O: -0.9 ± 0.4‰) indicating that changes in dietary δ13C and δ18O values of water are passed on to these fossilizing structures. A higher water temperature (20 °C) resulted in lower δ13C values in Daphnia and ephippia than in the other treatments with the same food source and in a minor change in the difference between δ13C values of ephippia and Daphnia (to -1.3 ± 0.3‰). This may have been due to microbial processes or increased algal respiration rates in the experimental containers, which may not affect Daphnia in natural environments. There was no significant difference in the offset between δ18O and δ15N values of ephippia and Daphnia between the 12 °C and 20 °C treatments, but the δ18O values of Daphnia and ephippia were on average 1.2‰ lower at 20 °C compared with 12 °C. We conclude

  1. Determination of the concentration and isotopic composition of uranium in environmental air filters

    SciTech Connect

    Russ, G.P. III; Bazan, J.M.

    1994-08-26

    For many years, Lawrence Livermore National Laboratory has collected monthly air-particulate filter samples from a variety of environmental monitoring stations on and off site. Historically the concentration and isotopic composition of uranium collected on these filters was determined by isotope dilution using a {sup 233}U spike and thermal ionization mass spectrometry (TIMS). For samples containing as little as 10 nanograms of uranium, ICP-MS is now used to make these measurements to the required level of precision, about 5% in the measured 235/238 and 233/238. Unless particular care is taken to control bias in the mass filter, variable mass bias limits accuracy to a few percent. Measurements of the minor isotopes 236 (if present) and 234 are also possible and provide useful information for identifying the source of the uranium. The advantage of ICP-MS is in rapid analysis, {approximately}12 minutes of instrument time per sample.

  2. The elemental and isotopic composition of quiet time low energy cosmic rays

    NASA Technical Reports Server (NTRS)

    Smith, B.; Mcdonald, F. B.

    1983-01-01

    Isotopic abundances during several periods of solar quiet times are derived from multidimensional analysis of double dE/dX modes made with two 150 micron dE detectors and a 3000 micron stopping E detector. The spectra of the low-energy cosmic rays suggest that all the primary species of elements exhibit flux enhancements. The flux increases of 5-12 MeV/N for C, Mg, Si, and Fe are different from the anomalous components and may result from solar contamination of the quiet time data or from interplanetary acceleration processes. They may be anomalous components (ACR), although to a lesser extent than He, N, O, and Ne. The isotopic data indicate that the ACR component is predominantly N-14, O-16, and Ne-20. The isotopic compositions require that the ACRs have traversed a very limited amount of material, suggesting a local origin for them.

  3. Carbon isotope composition of low molecular weight hydrocarbons and monocarboxylic acids from Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Yuen, G.; Blair, N.; Des Marais, D. J.; Chang, S.

    1984-01-01

    Carbon isotopic compositions have been measured for individual hydrocarbons and monocarboxylic acids from the Murchison meteorite, a C2 carbonaceous chondrite which fell in Australia in 1969. With few exceptions, notably benzene, the volatile products are substantially isotopically heavier than their terrestrial counterparts, signifying their extraterrestrial origin. For both classes of compounds, the ratio of C-13 to C-12 decreases with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic ratio than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with the kinetically controlled synthesis of higher homologues from lower ones. The results suggest the possibility that the production mechanisms for hydrocarbons and carboxylic acids may be similar, and impose constraints on the identity of the reactant species.

  4. Stable isotope and chemical compositions of European and Australasian ciders as a guide to authenticity.

    PubMed

    Carter, James F; Yates, Hans S A; Tinggi, Ujang

    2015-01-28

    This paper presents a data set derived from the analysis of bottled and canned ciders that may be used for comparison with suspected counterfeit or substitute products. Isotopic analysis of the solid residues from ciders (predominantly sugar) provided a means to determine the addition of C4 plant sugars. The added sugars were found to comprise cane sugar, high-fructose corn syrup, glucose, or combinations. The majority of ciders from Australia and New Zealand were found to contain significant amounts of added sugar, which provided a limited means to distinguish these ciders from European ciders. The hydrogen and oxygen isotopic compositions of the whole ciders (predominantly water) were shown to be controlled by two factors, the water available to the parent plant and evaporation. Analysis of data derived from both isotopic and chemical analysis of ciders provided a means to discriminate between regions and countries of manufacture. PMID:25536876

  5. Isotopic compositions of bismuth, lead, thallium, and mercury from mini r-processing

    NASA Technical Reports Server (NTRS)

    Heymann, D.; Liffman, K.

    1986-01-01

    The yields of stable isotopes of Bi, Pb, Tl and Hg as well as yields of Pb-205 are calculated with a parametrized model for 'mini r-processing' in the Ne, O, C-rich zones of explosive burning in massive stars. The Pb isotopic compositions stand out by their comparatively low Pb-207 yields and by the fact that this r-process variant yields Pb-204 quite abundantly. The average Pb-205/Pb-204 yield ratio of 6.1 is the same order of magnitude as yield ratios deduced for s-processing. The Hg from this mini r-process looks like normal solar-system mercury, but with Hg-196 missing and the light s-isotopes A = 198, 199, 200 and 201 depleted (especially the odd-A species).

  6. Isotopic composition of Antarctic Dry Valley nitrate: Implications for NOy sources and cycling in Antarctica

    USGS Publications Warehouse

    Michalski, G.; Bockheim, J.G.; Kendall, C.; Thiemens, M.

    2005-01-01

    Nitrates minerals from the Dry Valleys of Antarctica have been analyzed for their oxygen and nitrogen isotopic compositions. The 15N was depleted with ??15N values ranging from -9.5 to -26.2???, whereas the 17O and 18O isotopes were highly enriched (with excess 17O) with ?? 18O values spanning 62-76??? and ?? 17O values from 28.9 to 32.7???. These are the largest 17O enrichments observed in any known mineral. The oxygen isotopes indicate that nitrate is from a combination of tropospheric transport of photochemically produced HNO3 and HNO3 formed in the stratosphere. Copyrigbt 2005 by the American Geophysical Union.

  7. The Sulfur Isotope Composition of the Pyrite Burial Flux in the Modern Ocean

    NASA Astrophysics Data System (ADS)

    Turchyn, A. V.; Antler, G.; Byrne, D. J.; Sun, X.

    2014-12-01

    Microbial sulfate reduction followed by sulfide mineral burial, typically as pyrite, represents the largest removal pathway for sulfur from the exogenic sulfur reservoir. During microbial sulfate reduction, sulfur isotopes are partitioned such that the lighter 32S isotope is preferentially reduced; the magnitude of this partitioning has a large range (0 to 72‰), and therefore the average sulfur isotope composition of the global pyrite burial flux remains enigmatic. Recent work has mapped the global spatial distribution of microbial sulfate reduction rates in the modern ocean, which allows conclusions to be drawn concerning the conditions and controls on where sulfate respiration occurs (Bowles et al., 2014). The local rate of sulfate reduction in a particular sediment column can be calculated by the change in sulfate concentrations in pore fluids below the surface, which yields the net flux of sulfate into marine sediments. A flux of sulfate into the sediment is assumed to be due to diffusion along a concentration gradient set up by the consumption of sulfate at depth. We have calculated the deep-sea rates of microbial sulfate reduction using over 700 drilling sites and arrive at a similar estimate of the global modern rate of sulfate respiration. Rates of sulfate reduction are not, however, the same as the rates of pyrite burial, which is likely limited to the uppermost sediments where reactive iron may be available, or in the most nearshore environments where the terrestrial supply of iron is high and rates of sulfate reduction are orders of magnitude higher than those in the deep-sea. Sulfur isotope fractionation during microbial sulfate reduction is a function of several environmental factors, including the rate of sulfate reduction. We use a new compilation of the link between sulfate reduction rate and sulfur isotope fractionation with a model of pyrite burial in a range of modern marine sediments to derive an estimate of the global pyrite burial flux and

  8. Extreme Hf-Os Isotope Compositions in Hawaiian Peridotite Xenoliths: Evidence for an Ancient Recycled Lithosphere

    NASA Astrophysics Data System (ADS)

    Bizimis, M.; Lassiter, J. C.; Salters, V. J.; Sen, G.; Griselin, M.

    2004-12-01

    We report on the first combined Hf-Os isotope systematics of spinel peridotite xenoliths from the Salt Lake Crater (SLC), Pali and Kaau (PK) vents from the island of Oahu, Hawaii. These peridotites are thought to represent the Pacific oceanic lithosphere beneath Oahu, as residues of MORB-type melting at a paleo-ridge some 80-100Ma ago. Clinopyroxene mineral separates in these peridotites have very similar Nd and Sr isotope compositions with the post erosional Honolulu Volcanics (HV) lavas that bring these xenoliths to the surface. This and their relatively elevated Na and LREE contents suggest that these peridotites are not simple residues of MORB-type melting but have experience some metasomatic enrichment by the host HV lavas. However, the SLC and PK xenoliths show an extreme range in Hf isotope compositions towards highly radiogenic values (ɛ Hf= 7-80), at nearly constant Nd isotope compositions (ɛ Nd= 7-10), unlike any OIB or MORB basalt. Furthermore, these Oahu peridotites show a bimodal distribution in their bulk rock 187Os/186Os ratios: the PK peridotites have similar ratios to the abyssal peridotites (0.130-0.1238), while the SLC peridotites have highly subchondritic ratios (0.1237-0.1134) that yield 500Ma to 2Ga Re-depletion ages. Hf-Os isotopes show a broad negative correlation whereby the samples with the most radiogenic 176Hf/177Hf have the most unradiogenic 187Os/186Os ratios. Based on their combined Hf-Os-Nd isotope and major element compositions, the PK peridotites can be interpreted as fragments of the Hawaiian lithosphere, residue of MORB melting 80-100Ma ago, that have been variably metasomatized by the host HV lavas. In contrast, the extreme Hf-Os isotope compositions of the SLC peridotites suggest that they cannot be the source nor residue of any kind of Hawaiian lavas, and that Hf and Os isotopes survived the metasomatism or melt-rock reaction that has overprinted the Nd and Sr isotope compositions of these peridotites. The ancient (>1Ga

  9. Fe and O isotope composition of meteorite fusion crusts: Possible natural analogues to chondrule formation?

    NASA Astrophysics Data System (ADS)

    Hezel, Dominik C.; Poole, Graeme M.; Hoyes, Jack; Coles, Barry J.; Unsworth, Catherine; Albrecht, Nina; Smith, Caroline; RehkäMper, Mark; Pack, Andreas; Genge, Matthew; Russell, Sara S.

    2015-02-01

    Meteorite fusion crust formation is a brief event in a high-temperature (2000-12,000 K) and high-pressure (2-5 MPa) regime. We studied fusion crusts and bulk samples of 10 ordinary chondrite falls and 10 ordinary chondrite finds. The fusion crusts show a typical layering and most contain vesicles. All fusion crusts are enriched in heavy Fe isotopes, with δ56Fe values up to +0.35‰ relative to the solar system mean. On average, the δ56Fe of fusion crusts from finds is +0.23‰, which is 0.08‰ higher than the average from falls (+0.15‰). Higher δ56Fe in fusion crusts of finds correlate with bulk chondrite enrichments in mobile elements such as Ba and Sr. The δ56Fe signature of meteorite fusion crusts was produced by two processes (1) evaporation during atmospheric entry and (2) terrestrial weathering. Fusion crusts have either the same or higher δ18O (0.9-1.5‰) than their host chondrites, and the same is true for Δ17O. The differences in bulk chondrite and fusion crust oxygen isotope composition are explained by exchange of oxygen between the molten surface of the meteorites with the atmosphere and weathering. Meteorite fusion crust formation is qualitatively similar to conditions of chondrule formation. Therefore, fusion crusts may, at least to some extent, serve as a natural analogue to chondrule formation processes. Meteorite fusion crust and chondrules exhibit a similar extent of Fe isotope fractionation, supporting the idea that the Fe isotope signature of chondrules was established in a high-pressure environment that prevented large isotope fractionations. The exchange of O between a chondrule melt and an 16O-poor nebula as the cause for the observed nonmass dependent O isotope compositions in chondrules is supported by the same process, although to a much lower extent, in meteorite fusion crusts.

  10. Intraskeletal isotopic compositions (δ(13) C, δ(15) N) of bone collagen: nonpathological and pathological variation.

    PubMed

    Olsen, Karyn C; White, Christine D; Longstaffe, Fred J; von Heyking, Kristin; McGlynn, George; Grupe, Gisela; Rühli, Frank J

    2014-04-01

    Paleodiet research traditionally interprets differences in collagen isotopic compositions (δ(13) C, δ(15) N) as indicators of dietary distinction even though physiological processes likely play some role in creating variation. This research investigates the degree to which bone collagen δ(13) C and δ(15) N values normally vary within the skeleton and examines the influence of several diseases common to ancient populations on these isotopic compositions. The samples derive from two medieval German cemeteries and one Swiss reference collection and include examples of metabolic disease (rickets/osteomalacia), degenerative joint disease (osteoarthritis), trauma (fracture), infection (osteomyelitis), and inflammation (periostitis). A separate subset of visibly nonpathological skeletal elements from the German collections established normal intraindividual variation. For each disease type, tests compared bone lesion samples to those near and distant to the lesions sites. Results show that normal (nonpathological) skeletons exhibit limited intraskeletal variation in carbon- and nitrogen-isotope ratios, suggesting that sampling of distinct elements is appropriate for paleodiet studies. In contrast, individuals with osteomyelitis, healed fractures, and osteoarthritis exhibit significant intraskeletal differences in isotope values, depending on whether one is comparing lesions to near or to distant sites. Skeletons with periostitis result in significant intraskeletal differences in nitrogen isotope values only, while those with rickets/osteomalacia do not exhibit significant intraskeletal differences. Based on these results, we suggest that paleodiet researchers avoid sampling collagen at or close to lesion sites because the isotope values may be reflecting both altered metabolic processes and differences in diet relative to others in the population. PMID:24374993

  11. Record of seasonal body fluid composition in Black Clam (Bivalve) using clumped isotope thermometric approach

    NASA Astrophysics Data System (ADS)

    Rahman, H.; Naidu, P. K.; Ghosh, P.

    2012-12-01

    Application of clumped isotope thermometry (Ghosh et al., 2006) is highly debated while resolving the issue of kinetic effect during biogenic carbonate precipitation. Mollusks are particularly attractive target to study the kinetic effect (Eiler, 2011) in the biological system owing to its incremental growth ring patterns. This allows understanding the role of environmental parameters other than temperature driving the distribution of heavier isotopologues. Guo et al., (2010) indicated role of pH in driving the distribution of heavier isotopolgues in the carbonates. We investigated here clumped isotopic composition of Black Calm (bivalve shell) caught live from a location in Southern Indian Estuary. The region experiences large change in seasonal condition. The physical environmental parameters at that location were monitored for last 3 years at monthly interval. The salinity, temperature, pH information are available for all the months when mollusc growth bands are deposited. The bottom water of estuary, where bivalve thrives experience maximum temperature of 32°C during November and December, while temperature during Monsoon months (July, August) drops lows to 26°C. Initial results on clumped isotope thermometry on the growth bands precipitated suggests that during the time in a year when pH level is alkaline i.e. 8.0±0.2 there is large consistency between actual temperature and estimated temperature using clumped isotope based thermometry. While the pH drops towards acidic i.e. 6.8±0.1 lower temperature estimates compared to actual was recorded. The effect of metabolic rate and body temperature variability is not been investigated as suggested in case of land snails based clumped isotope thermometry (Zaarur et al., 2011). Mollusc shell can be used to trace the composition of environmental water while pH variation is minimal. In this presentation analyses of more shell specimen and explore the role of pH and osmo-regulation in mollusc determining the clumped

  12. New views on the isotopic composition of atmospheric oxygen

    NASA Astrophysics Data System (ADS)

    Luz, B.

    2001-05-01

    Air oxygen is enriched in O-18 with respect to ocean water by about 23 permil. This enrichment is named "Dole effect" after its discoverer. Air oxygen originates from marine and terrestrial photosynthesis that produces oxygen gas without fractionation with respect to the substrate water. The O-18 enrichment results primarily from preferential removal of O-16 during respiratory uptake. However, the discrimination against O-18 in ordinary dark respiration is only 18 permil, and cannot account for the entire magnitude of the Dole effect. Part of the discrepancy may be explained by enrichment of the substrate water in terrestrial evapo-transpiration. But the existing evidence on the magnitude of this enrichment shows that this mechanism alone cannot explain the discrepancy. In an attempt to better understand the Dole effect we have studied the overall fractionation in soil and aquatic oxygen uptake. Due to slow gas diffusion in soils and roots the discrimination is smaller than in respiration. This result thus increases the discrepancy. On the other hand, our new estimates show that discrimination in aquatic oxygen uptake is considerably greater than previously assumed. Oxygen uptake in the surface waters of oceans and lakes takes place by ordinary dark respiration as well as by cyanide resistant respiration in both dark and light conditions, and by photorespiration and Mehler reaction that occur only during illumination. Thus in order to study the overall discrimination in aquatic systems it is necessary to evaluate its effects in both light and dark conditions and to separate the effect of photosynthetic production of oxygen. Such separation is possible if gross rates of oxygen production and consumption are known. We have estimated these rates from in situ incubation experiments and from the natural distribution of O-16, O-17, O-18 and the ratio of dissolved oxygen/argon. We have used isotopic and elemental budgets to derive the overall respiratory fractionation in

  13. Stable isotope study of a new chondrichthyan fauna (Kimmeridgian, Porrentruy, Swiss Jura): an unusual freshwater-influenced isotopic composition for the hybodont shark Asteracanthus

    NASA Astrophysics Data System (ADS)

    Leuzinger, L.; Kocsis, L.; Billon-Bruyat, J.-P.; Spezzaferri, S.; Vennemann, T.

    2015-12-01

    Chondrichthyan teeth (sharks, rays, and chimaeras) are mineralized in isotopic equilibrium with the surrounding water, and parameters such as water temperature and salinity can be inferred from the oxygen isotopic composition (δ18Op) of their bioapatite. We analysed a new chondrichthyan assemblage, as well as teeth from bony fish (Pycnodontiformes). All specimens are from Kimmeridgian coastal marine deposits of the Swiss Jura (vicinity of Porrentruy, Ajoie district, NW Switzerland). While the overall faunal composition and the isotopic composition of bony fish are generally consistent with marine conditions, unusually low δ18Op values were measured for the hybodont shark Asteracanthus. These values are also lower compared to previously published data from older European Jurassic localities. Additional analyses on material from Solothurn (Kimmeridgian, NW Switzerland) also have comparable, low-18O isotopic compositions for Asteracanthus. The data are hence interpreted to represent a so far unique, freshwater-influenced isotopic composition for this shark that is classically considered a marine genus. While reproduction in freshwater or brackish realms is established for other hybodonts, a similar behaviour for Asteracanthus is proposed here. Regular excursions into lower salinity waters can be linked to the age of the deposits and correspond to an ecological adaptation, most likely driven by the Kimmeridgian transgression and by the competition of the hybodont shark Asteracanthus with the rapidly diversifying neoselachians (modern sharks).

  14. Stable isotope study of a new chondrichthyan fauna (Kimmeridgian, Porrentruy, Swiss Jura): an unusual freshwater-influenced isotopic composition for the hybodont shark Asteracanthus

    NASA Astrophysics Data System (ADS)

    Leuzinger, L.; Kocsis, L.; Billon-Bruyat, J.-P.; Spezzaferri, S.; Vennemann, T.

    2015-08-01

    Chondrichthyan teeth (sharks, rays and chimaeras) are mineralised in isotopic equilibrium with the surrounding water, and parameters such as water temperature and salinity can be inferred from the oxygen isotopic composition (δ18Op) of their bioapatite. We analysed a new chondrichthyan assemblage, as well as teeth from bony fish (Pycnodontiformes). All specimens are from Kimmeridgian coastal marine deposits of the Swiss Jura (vicinity of Porrentruy, Ajoie district, NW Switzerland). While the overall faunal composition and the isotopic composition of bony fish are consistent with marine conditions, unusually low δ18Op values were measured for the hybodont shark Asteracanthus. These values are also lower compared to previously published data from older European Jurassic localities. Additional analyses on material from Solothurn (Kimmeridgian, NW Switzerland) also have comparable, low-18O isotopic compositions for Asteracanthus. The data are hence interpreted to represent a so far unique, freshwater-influenced isotopic composition for this shark that is classically considered as a marine genus. While reproduction in freshwater or brackish realms is established for other hybodonts, a similar behaviour for Asteracanthus is proposed here. Regular excursions into lower salinity waters can be linked to the age of the deposits and correspond to an ecological adaptation, most likely driven by the Kimmeridgian transgression and by the competition of the primitive shark Asteracanthus with the rapidly diversifying neoselachians (modern sharks).

  15. Recent planktic foraminifers in the Fram Strait (Arctic Ocean): carbon and oxygen stable isotope composition

    NASA Astrophysics Data System (ADS)

    Pados, T.; Spielhagen, R. F.; Bauch, D.; Meyer, H.; Segl, M.

    2012-12-01

    In paleoceanographic reconstructions the carbon isotopic compositions (δ13C) of fossil foraminifers refer to, e.g., paleoproductivity and stratification, while oxygen isotopic (δ18O) records provide information about variations in sea surface temperatures and salinities in the past. However, for a correct interpretation of the fossil data it is important to improve our understanding of the correlation between recent oceanic variability and the composition of shells of living calcareous microorganisms. For this, the upper water column and sediment surface in the Fram Strait (Arctic Ocean, 78°50'N, 5°W-8°E) were sampled for planktic foraminifer species Neogloboquadrina pachyderma (sin.) and Turborotalita quinqueloba with a large-diameter multinet and a multicorer, respectively. The δ13C and δ18O values of the shells are compared to the stable isotope composition of the ambient water and to equilibrium calcite values to define the preferred calcification depths of the foraminifers and to determine the factors controlling the isotopic signature of these calcareous microorganisms. The study area was chosen because of its high oceanographic variability: in the eastern Fram Strait the northward flowing West Spitsbergen Current (WSC) carries Atlantic Water, with a thin mixed layer on top, while in the west the upper 200 m consists of cold, low-saline Arctic outflow waters of the East Greenland Current (EGC) and warmer, saline waters of Atlantic origin underneath. Despite this variable oceanographic regime along the studied transect, the stable carbon isotope ratios of the shells do not show major differences according to their horizontal but to their vertical distribution: the δ13C values of N. pachyderma (sin.) from plankton tow samples vary roughly between -1 and -0.1‰ depending on the water depth, while the δ18O values of the tests differ more between the stations.

  16. Anthropogenic Pb input into Bohai Bay, China: Evidence from stable Pb isotopic compositions in sediments

    NASA Astrophysics Data System (ADS)

    Hu, Ningjing; Huang, Peng

    2016-04-01

    Anthropogenic Pb input into Bohai Bay, China: Evidence from stable Pb isotopic compositions in sediments Hu Ning-jinga, Huang Pengb,, Liu Ji-huaa, a First Institute of Oceanography, State Oceanic Administration, Qingdao 266061, China b Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071, China To investigate the source of Pb within Bohai Bay, Pb concentrations and Pb isotopic compositions (204Pb, 206Pb, 207Pb, and 208Pb) of surface sediments in this area were determined. The Pb concentration in this bay varied widely from 6.9 to 39.2 μg/g (average: 21.8 ± 7.8 μg/g), and the Pb isotopic compositions ranged from 0.8338 to 0.8864 (average: 2.0997 ± 0.0180) for 208Pb/206Pb and from 2.0797 to 2.1531 (average: 0.8477 ± 0.0135) for 207Pb/206Pb, presenting in three distinct clusters. The Pb isotopic ratios of sediments from the northeastern (NE zone) and northwestern (NW zone) coastal areas were significantly influenced by anthropogenic sources such as coal combustion and automobile emission. In sediments from the central and southern Bohai Bay (C-S zone); however, Pb mainly originated from the Yellow River catchment, as a result of lithogenic sediment (from rock weathering) accumulation. The Pb isotopic ratios further indicate that, apart from riverine inputs, the neighboring large-scale ports and aerosols significantly contributed to the anthropogenic Pb contained in these sediments. Pb contamination in the Haihe and Luanhe river mouths as well as in the regions near ports is also suggested from anthropogenic enrichment factors. As cities and ports continue to develop around Bohai Bay, a long-term extensive sewage monitoring program is highly recommended.

  17. Reconstructing Cambro-Ordovician Seawater Composition using Clumped Isotope Paleothermometry on Calcitic and Phosphatic Brachiopods

    NASA Astrophysics Data System (ADS)

    Bergmann, K.; Robles, M.; Finnegan, S.; Hughes, N. C.; Eiler, J. M.; Fischer, W. W.

    2012-12-01

    A secular increase in δ18O values of marine fossils through early Phanerozoic time raises questions about the evolution of climate and the water cycle. This pattern suggests two end-member hypotheses 1) surface temperatures during early Paleozoic time were very warm, in excess of 40°C (tropical MAT), or 2) the isotopic composition of seawater increased by up to 7-8‰. It has been difficult to evaluate these hypotheses because the δ18O composition of fossils depends on both temperature and the δ18O of water. Furthermore, primary isotopic signatures can be overprinted by diagenetic processes that modify geological materials. This too could explain the decrease in δ18O values of marine fossils with age. Carbonate clumped isotope thermometry can constrain this problem by providing an independent measure of crystallization temperature and, when paired with classical δ18O paleothermometry, can determine the isotopic composition of the fluid the mineral last equilibrated with. Combined with traditional tools, this method has the potential to untangle primary isotopic signatures from diagenetic signals. We measured the isotopic ordering of CO3 groups (Δ47) substituted into the phosphate lattice of phosphatic brachiopods in Cambrian strata. Phosphatic fossils are generally less soluble than carbonates in surface and diagenetic environments, and so are hypothesized to provide a more robust record of primary growth conditions. They also provide an archive prior to the rise of thick shelled calcitic fossils during the Ordovician Radiation. Additionally, measurements of the δ18O of the CO3 groups can be compared with the δ18O of PO4 groups to test whether their mutual fractionation is consistent with primary growth and the apparent temperature recorded by carbonate clumped isotope measurements. We are constructing a phosphatic brachiopod calibration for carbonate clumped isotope thermometry, and Δ47 values of CO2 extracted from modern phosphatic brachiopods suggest

  18. Sulfide isotopic compositions in shergottites and ALH84001, and possible implications for life on Mars

    SciTech Connect

    Greenwood, J.P.; McSween, H.Y. Jr.; Riciputi, L.R.

    1997-10-01

    The shergottite and ALH84001 meteorites hold keys for understanding geologic and possibly biologic processes on Mars. Recently, it has been proposed that carbonates in ALH84001, and the Fe-sulfides they contain, are products of extraterrestrial biogenic activity. Here we report ion microprobe analyses of sulfides in shergottites and ALH84001. The sulfur isotope ratios of igneous pyrrhotites in shergottites (mean {delta}{sup 34}S{sub CDT}: Shergotty = -0.4{per_thousand}, Zagami = +2.7{per_thousand}, EETA79001A = 1.9{per_thousand}, EETA79001B = -1.7{per_thousand}, LEW88516 = -1.9{per_thousand}, QUE94201 = +0.8{per_thousand}) are similar to those of terrestrial ocean-floor basalts, suggesting that the sulfur isotopic composition of the Martian mantle may be similar to that of the mantle of the Earth. The sulfur isotopic systematics of ALH84001 sulfides are distinct from the shergottites. Measured sulfur isotope ratios of eight pyrite grains ({delta}{sup 34}S{sub CDT} = +2.0 to +7.3{per_thousand}) in crushed zones confirm previously reported analyses of isotopically heavy sulfides and are indistinguishable from an Fe-sulfide zone within a carbonate globule ({delta}{sup 34}S{sub CDT} = +6.0{per_thousand}). Analyses of synthesized, fine-grained mixtures of sulfide, carbonate, and magnetite indicate than the measured sulfur isotope ratio is independent of the presence of carbonate and magnetite in the sputtered volume, confirming the accuracy of the analysis of the fine-grained sulfide in the carbonate globule. Terrestrial biogenic sulfate reduction typically results in light isotopic enrichments. The similarity of {delta}{sup 34}S values of the sulfides in ALH84001 imply that the Fe-sulfide zones within ALH84001 carbonates are probably not the result of bacterial reduction of sulfate. 38 refs., 3 figs., 1 tab.

  19. Anthropogenic Pb input into Bohai Bay, China: Evidence from stable Pb isotopic compositions in sediments

    NASA Astrophysics Data System (ADS)

    Ning-jing, Hu; Peng, Huang; Hui, Zhang; Ai-mei, Zhu; Ji-hua, Liu; Jun, Zhang; Lian-hua, He

    2015-10-01

    To investigate the source of Pb within Bohai Bay, Pb concentrations and Pb isotopic compositions (204Pb, 206Pb, 207Pb, and 208Pb) of surface sediments in this area were determined. The Pb concentration in this bay varied widely from 6.9 to 39.2 μg/g (average: 21.8±7.8 μg/g), and the Pb isotopic compositions ranged from 0.8338 to 0.8864 (average: 2.0997±0.0180) for 208Pb/206Pb and from 2.0797 to 2.1531 (average: 0.8477±0.0135) for 207Pb/206Pb, presenting in three distinct clusters. The Pb isotopic ratios of sediments from the northeastern (NE zone) and northwestern (NW zone) coastal areas were significantly influenced by anthropogenic sources such as coal combustion and automobile emission. In sediments from the central and southern Bohai Bay (C-S zone); however, Pb mainly originated from the Yellow River catchment, as a result of lithogenic sediment (from rock weathering) accumulation. The Pb isotopic ratios further indicate that, apart from riverine inputs, the neighboring large-scale ports and aerosols significantly contributed to the anthropogenic Pb contained in these sediments. Pb contamination in the Haihe and Luanhe river mouths as well as in the regions near ports is also suggested from anthropogenic enrichment factors. As cities and ports continue to develop around Bohai Bay, a long-term extensive sewage monitoring program is highly recommended.

  20. Lead isotope and trace element composition of urban soils in Mongolia

    NASA Astrophysics Data System (ADS)

    Tserenpil, Sh.; Sapkota, A.; Liu, C.-Q.; Peng, J.-H.; Liu, B.; Segebade, P. Chr.

    2016-08-01

    Lead (Pb) pollution in and around Ulaanbaatar is of national concern, given that the Mongolian capital is home to nearly half of the country's entire population. By comparison, Mongolian countryside is a pristine environment because of its sparse population and low industrial activity. The concentration of Pb in urban soils (average of 39.1 mg kg-1) was twice the values found (average 18.6 mg kg-1) in background territories (i.e., Mongolian rural sites). Furthermore, Pb contamination was examined by using Pb stable isotopic composition, and covariance of Pb isotopic ratios showed two groups between rural and urban soils as pristine and disturbed sites. The 206Pb/207Pb ratio, the most prominent fingerprint for Pb pollution, was 1.163-1.185 for the urban whereas values for rural soils (1.186-1.207) were analogue to the regional Pb isotopic signatures. Local coal sources and their combustion products, one of the potential Pb pollution sources in Ulaanbaatar, have significant radiogenic properties in terms of Pb isotopic composition and revealed an average of 1.25 for 206Pb/207Pb and 19.551 for 206Pb/204Pb ratios. Thus, contributions from coal firing activity to Pb pollution lower than it was assumed, and smaller range of these values measured in urban soils may be attributed to the mixing of less radiogenic Pb as a constituent of the leaded gasolines.

  1. Effect of storage on the isotopic composition of nitrate in bulk precipitation.

    PubMed

    Spoelstra, John; Schiff, Sherry L; Jeffries, Dean S; Semkin, Ray G

    2004-09-15

    Stable isotopic analysis of atmospheric nitrate is increasingly employed to study nitrate sources and transformations in forested catchments. Large volumes have typically been required for delta18O and delta15N analysis of nitrate in precipitation due to relatively low nitrate concentrations. Having bulk collectors accumulate precipitation over an extended time period allows for collection of the required volume as well as reducing the total number of analyses needed to determine the isotopic composition of mean annual nitrate deposition. However, unfiltered precipitation left in collectors might be subject to microbial reactions that can alter the isotopic signature of nitrate in the sample. Precipitation obtained from the Turkey Lakes Watershed was incubated under conditions designed to mimic unfiltered storage in bulk precipitation collectors and monitored for changes in nitrate concentration, delta15N, and delta18O. Results of this experiment indicated that no detectable nitrate production or assimilation occurred in the samples during a two-week incubation period and that atmospheric nitrate isotopic ratios were preserved. The ability to collect unfiltered precipitation samples for an extended duration without alteration of nitrate isotope ratios is particularly useful at remote study sites where daily retrieval of samples may not be feasible. PMID:15487778

  2. Neoproterozoic variations in the C-isotopic composition of seawater: stratigraphic and biogeochemical implications

    NASA Technical Reports Server (NTRS)

    Kaufman, A. J.; Knoll, A. H.

    1995-01-01

    The recent proliferation of stratigraphic studies of delta 13C variation in carbonates and organic C in later Neoproterozoic and basal Cambrian successions (approximately 850-530 Ma) indicates a strong oscillating trend in the C-isotopic composition of surface seawater. Alone, this trend does not adequately characterize discrete intervals in Neoproterozoic time. However, integrated with the vectorial signals provided by fossils and Sr-isotopic variations, C isotope chemostratigraphy facilitates the interbasinal correlation of later Neoproterozoic successions. Results of these studies are evaluated in terms of four stratigraphic intervals: (1) the Precambrian/Cambrian boundary, (2) the post-Varanger terminal Proterozoic, (3) the late Cryogenian, and (4) the early Cryogenian. Where biostratigraphic or radiometric data constrain the age of Neoproterozoic sedimentary sequences, secular variations in C and Sr isotopes can provide a level of stratigraphic resolution exceeding that provided by fossils alone. Isotopic data place strong constraints on the chemical evolution of seawater, linking it to major tectonic and paleoclimatic events. They also provide a biogeochemical framework for the understanding of the initial radiation of macroscopic metazoans, which is associated stratigraphically, and perhaps causally, with a global increase in the burial of organic C and a concomitant rise of atmospheric O2.

  3. Spacial and temporal variation of H and O isotopic compositions of the Xijiang Rivers System

    NASA Astrophysics Data System (ADS)

    Han, G.

    2015-12-01

    Pin Lv1, Fushan Li2, Yang Tang2 School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing 10083, China The State Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550002, China The H and O isotope compositions in the Xijiang River water was investigated on the sample collected from the mainstream and main tributaries in Aug. 2014 and in Jan. 2015. Large variation ranges were observed for δD with (-35.3‰ to -77.1‰ in summer, -31.3‰ to -76.6‰ in winter) andδ18O (-4.8‰ to -10.3‰ in summer, -4.5‰ to -10.3‰ in winter). From the river head to the river mouth, the H and O isotope compositions of the river water collected in the high-discharge and low-discharge period display always a similar variation pattern. On the basis of isotopic composition of river water, the Xijiang River may be separated by three subbasins including the upper basin, the middle basin and the lower basin. The upper reached river water contains relatively low values of δD and δ18O. The values of δD and δ18O in the middle reaches are quite variable because of the middle basin severely disturbed through water impoundments. The lower reaches river water contains high values of δD and δ18O. The differences of δD and δ18O compositions between various tributaries and its effect to the δD and δ18O of the mainstream reflects also the constraint of the meteoric water to the Xijiang River. Evaporation has also important effect to the H and O isotope compositions of the Xijiang River, and it is found that evaporation can also raise the δD and δ18O values of the water during the dry season. Our investigation indicates that the H and O isotope tracing method can play a key role in studying the interaction between river water and other waters, such as the meteoric water, underground water, and lake water. The combination of proper H and O isotope study with conventional meteoric and

  4. Lead Isotopic Compositions of the Endeavour Sulfides, Juan de Fuca Ridge

    NASA Astrophysics Data System (ADS)

    Labonte, F.; Hannington, M. D.; Cousens, B. L.; Blenkinsop, J.; Gill, J. B.; Kelley, D. S.; Lilley, M. D.; Delaney, J. R.

    2006-12-01

    32 sulfide samples from the main structures of the Endeavour vent field, Juan de Fuca Ridge, were analyzed for their Pb isotope composition. The samples were collected from 6 main vent fields between 1985 and 2005 and encompass a strike length of more than 15 km along the ridge crest. The sulfides are typical of black smoker deposits on sediment-starved mid-ocean ridges. Pb isotope compositions of the massive sulfides within the six hydrothermal fields vary within narrow ranges, with 206Pb/204Pb = 18.58 18.75, 207Pb/204Pb = 15.45 15.53 and 208Pb/204Pb = 37.84 38.10. A geographic trend is observed, with the lower Pb ratios restricted mostly to the northern part of the segment (Salty Dawg, Sasquatch and High Rise fields), and the higher Pb ratios restricted mostly to the southern part of the segment (Main Endeavour, Clam Bed and Mothra fields). Variations within individual fields are much smaller than those between fields, and variation within individual sulfide structures is within the uncertainty of the measurements. Therefore, it is unlikely that the ranges of Pb isotope compositions along the length of the segment reflect remobilization, replacement, and recrystallization of sulfides, as suggested for the observed Pb isotope variability in some large seafloor sulfide deposits. Instead, the differences in isotopic compositions from north to south are interpreted to reflect differences in the source rocks exposed to hydrothermal circulation of fluids below the seafloor. Possible sources of the somewhat more radiogenic Pb may be small amounts of buried sediment, either from turbidites or from hemipelagic sediment. This possibility is supported by high concentrations of CH4 and NHC4 found in the high-temperature vent fluids at the Main Endeavour Field, which are interpreted to reflect subseafloor interaction between hydrothermal fluids and organic material in buried sediments. However, the majority of the samples fall below and are approximately parallel to the

  5. Hydrogen isotope composition of leaf wax n-alkanes in Arabidopsis lines with different transpiration rates

    NASA Astrophysics Data System (ADS)

    Pedentchouk, N.; Lawson, T.; Eley, Y.; McAusland, L.

    2012-04-01

    Stable isotopic compositions of oxygen and hydrogen are used widely to investigate modern and ancient water cycles. The D/H composition of organic compounds derived from terrestrial plants has recently attracted significant attention as a proxy for palaeohydrology. However, the role of various plant physiological and biochemical factors in controlling the D/H signature of leaf wax lipids in extant plants remains unclear. The focus of this study is to investigate the effect of plant transpiration on the D/H composition of n-alkanes in terrestrial plants. This experiment includes 4 varieties of Arabidopsis thaliana that differ with respect to stomatal density and stomatal geometry. All 4 varieties were grown indoors under identical temperature, relative humidity, light and watering regimes and then sampled for leaf wax and leaf water stable isotopic measurements. During growth, stomatal conductance to carbon dioxide and water vapour were also determined. We found that the plants varied significantly in terms of their transpiration rates. Transpiration rates were significantly higher in Arabidopsis ost1 and ost1-1 varieties (2.4 and 3.2 mmol m-2 s-1, respectively) than in Arabidopsis RbohD and Col-0 (1.5 and 1.4). However, hydrogen isotope measurements of n-alkanes extracted from leaf waxes revealed a very different pattern. Varieties ost1, ost1-1, and RbohD have very similar deltaD values of n-C29 alkane (-125, -128, and -127 per mil), whereas the deltaD value of Col-0 is more negative (-137 per mil). The initial results of this work suggest that plant transpiration is decoupled from the D/H composition of n-alkanes. In other words, physical processes that affect water vapour movement between the plant and its environment apparently cannot account for the stable hydrogen isotope composition of organic compounds that comprise leaf waxes. Additional, perhaps biochemical, processes that affect hydrogen isotope fractionation during photosynthesis might need to be invoked

  6. Stable chromium isotopic composition of meteorites and metal-silicate experiments: Implications for fractionation during core formation

    NASA Astrophysics Data System (ADS)

    Bonnand, P.; Williams, H. M.; Parkinson, I. J.; Wood, B. J.; Halliday, A. N.

    2016-02-01

    We present new mass independent and mass dependent Cr isotope compositions for meteorites measured by double spike thermal ionisation mass spectrometry. Small differences in both mass independent 53Cr and 54Cr relative to the Bulk Silicate Earth are reported and are very similar to previously published values. Carbonaceous chondrites are characterised by an excess in 54Cr compared to ordinary and enstatite chondrites which make mass independent Cr isotopes a useful tool for distinguishing between meteoritic groups. Mass dependent stable Cr isotope compositions for the same samples are also reported. Carbonaceous and ordinary chondrites are identical within uncertainty with average δ53 Cr values of - 0.118 ± 0.040 ‰ and - 0.143 ± 0.074 ‰ respectively. The heaviest isotope compositions are recorded by an enstatite chondrite and a CO carbonaceous chondrite, both of which have relatively reduced chemical compositions implying some stable Cr isotope fractionation related to redox processes in the circumstellar disk. The average δ53 Cr values for chondrites are within error of the estimate for the Bulk Silicate Earth (BSE) also determined by double spiking. The lack of isotopic difference between chondritic material and the BSE provides evidence that Cr isotopes were not fractionated during core formation on Earth. A series of high-pressure experiments was also carried out to investigate stable Cr isotope fractionation between metal and silicate and no demonstrable fractionation was observed, consistent with our meteorites data. Mass dependent Cr isotope data for achondrites suggest that Cr isotopes are fractionated during magmatic differentiation and therefore further work is required to constrain the Cr isotopic compositions of the mantles of Vesta and Mars.

  7. Composition of fine and ultrafine particles and source identification by stable isotope ratios

    NASA Astrophysics Data System (ADS)

    Gone, Jec-Kong

    Fine (da < 2.1 μm) and ultra-fine (da < 0.1μm) atmosphere particulate samples collected from two sites in the United States were analyzed for elemental compositions by Instrumental, Neutron Activation Analysis (INAA) at Massachusetts Institute of Technology. The eastern site samples were collected at the Great Smoky Mountain National Park from July 15 to August 25, 1995. The western site samples were collected from a rooftop in Pasadena, California over one winter month in January/February, 1996. Elemental concentrations determined by INAA for the eastern site samples were compared with results from samples (da < 2.4 μm) collected concurrently but analyzed by other techniques. The results showed consistency between different analytical techniques. Factor Analysis (FA) and Absolute Factor Score-Multiple Linear Regression (AFS-MLR) methods were used to identify sources and their contributions to fine particulate samples at the eastern site. The results showed that the crustal contribution to fine aerosol mass was significant around July 24-26, 1995, and the coal combustion contribution peaked around August 14-18, 1995. The average contribution from crustal sources to the fine particulate mass was 7 +/- 3% for the 2.1 μm samples and 11 +/- 4% for the 2.4 μm samples. The mass difference may be due to the different maximum size of the particles. The average contribution from combustion sources was 77 +/- 4% for the 2.1 μm samples and 90 +/- 6% for the 2.4 μm samples. Elemental patterns were used to identify sources of ultra-fine particles. Motor vehicle emissions might be the cause of the increase in the ultra-fine particle concentration of Al and Fe at the western site. Variations in stable isotope ratios of 130Ba/138 Ba, 121Sb/123Sb, 84Sr/ 86Sr and 79Br/81Br were investigated using INAA. This technique was applied to fine particulate samples with sources identified by FA. The results showed that the 130Ba/ 138Ba ratio of the dust sample was 0.00151 +/- 0

  8. The isotopic composition of silver and lead in two iron meteorites - Cape York and Grant

    NASA Technical Reports Server (NTRS)

    Chen, J. H.; Wasserburg, G. J.

    1983-01-01

    Anomalies in silver isotope composition in the metal phases of the Cape York (IIIA) and Grant (IIIB) iron meteorites are studied together with the lead isotopic composition of both the metal and sulfide phases of Cape York. Following extensive surface cleaning, the Ag-107/Ag-109 ratio in the metal phases of the meteorites is found to be in excess of the terrestrial ratio, and of that found in the sulfide phases. A definite correlation between the Ag-107/Ag-109 and Pd-108/Ag-109 ratios is observed for these meteorites, indicating the in situ decay of Pd-107 and supporting the widespread presence of Pd in the early universe. Lead, determined after cleaning and with chemical separations using low blank levels, is found to exist in variable proportions in the metal and sulfide phases. The sulfides appear to be dominated by radiogenic modern lead, which may be explained by terrestrial contamination or by late metamorphism in the meteorite parent body.

  9. Chromium and Iron Isotopic Composition of Presolar Silicon Carbide Stardust Grains

    NASA Astrophysics Data System (ADS)

    Savina, M.; Levine, J.; Dauphas, N.; Pellin, M.; Willingham, D.; Stephan, T.; Trappitsch, R.; Davis, A. M.

    2011-12-01

    Most presolar SiC stardust grains derive from Asymptotic Giant Branch (AGB) stars, which are the main source of s-process nuclides in the galaxy. s-Process nucleosynthesis is not a major contributor to iron peak nuclides. The most interesting of these isotopes from an AGB nucleosynthetic standpoint are the trace isotopes 54Cr and 58Fe, which are predicted to have deviations from average Solar System ratios of ~100% and >200%, respectively. The other isotopes of Cr and Fe are essentially unchanged by AGB stars, and are representative of the isotopic composition of the protostellar cloud from which the SiC grains formed. They are thus tracers of Galactic Chemical Evolution, and provide a benchmark for the isotopic composition of the galaxy some five to seven billion years ago. SiC grains were isolated from the Murchison meteorite using high purity reagents and techniques specifically designed to prevent contamination with terrestrial Cr and Fe. Grains from the 2-4 μm size fraction were pressed into a high purity gold foil. Chromium and iron isotopic compositions were measured by Resonance Ionization Mass Spectrometry (RIMS) using new techniques specifically developed for high precision isotopic analysis of iron-peak elements. The Cr isotopic compositions of 19 grains form a distinct group. Several grains had resolvable (>2σ) 50Cr and 53Cr deficits ranging as low as -178%. The 54Cr/ 52Cr δ-values were all within 2σ of the Solar System value, though most were slightly higher. The average δ-values for the grains were -45±31% for 50Cr, -37±21% for 53Cr, and +25±26% for 54Cr. Iron results are pending. Given that AGB stars change most Fe and Cr isotope ratios very little, and that these grains' progenitor stars formed from a few hundred million to about three billion years before the Solar System formed (assuming their initial masses were 1.5 - 3 solar masses), and that grain interstellar residence times are likely less than ~100 - 200 million years, the Fe and Cr

  10. Atmospheric control on isotopic composition and d-excess in water vapor over ocean surface

    NASA Astrophysics Data System (ADS)

    Fan, Naixin

    For decades, stable isotopes of water have been used as proxies to infer the variation of the hydrological cycle. However, it is still not clear how various atmospheric processes quantitatively control kinetic fractionation during evaporation over the ocean. Understanding kinetic fractionation is important in that the interpretation of the isotopic composition record preserved in ice cores and precipitation relies in part on the isotopic information at the moisture source. In addition, the isotopic composition of vapor contains information about variation of atmospheric processes such as turbulence and change in moisture source region which is useful for studying meteorological processes and climate change. In this study the isotopic composition of water vapor in the marine boundary layer (MBL) over the ocean was investigated using a combination of a newly developed marine boundary layer (MBL) model and observational data. The new model has a more realistic MBL structure than previous models and includes new features such as vertical advection of air and diffusion coefficients that vary continuously in the vertical direction. A robust linear relationship between deltaD and delta18O was found in observational oceanic water vapor data and the model can well capture the characteristics of this relationship. The individual role of atmospheric processes or variables on deltaD, delta18O and d-excess was quantitatively investigated and an overview of the combined effect of all the meteorological processes is provided. In particular, we emphasize that the properties of subsiding air (such as its mixing ratio and isotopic values) are crucial to the isotopic composition of surface water vapor. Relative humidity has been used to represent the moisture deficit that drives evaporative isotopic fluxes, however, we argue that it has serious limitations in explaining d-excess variation as latitude varies. We introduce a new quantity Gd=SST-Td, the difference between the sea

  11. Microscale determination of the spectral characteristics and carbon-isotopic compositions of porphyrins

    NASA Technical Reports Server (NTRS)

    Popp, B. N.; Hayes, J. M.; Boreham, C. J.

    1993-01-01

    Molar extinction coefficients for band III of Ni porphyrins are calculated from results of spectrophotometric and manometric analyses of individual etioporphyrins, DPEP, cyclic, and diDPEP porphyrins known to initially be pure from mass spectrometry, 1H NMR, and analytical HPLC studies. A method for determining carbon-isotopic compositions and purity of micromolar quantities of individual porphyrins using combined spectrophotometric and manometric techniques is presented.

  12. U and Th Concentration and Isotopic Composition of Hydrothermal Fluids at the Lost City Hydrothermal Field

    NASA Astrophysics Data System (ADS)

    Ludwig, K. A.; Shen, C.; Cheng, H.; Edwards, R.; Kelley, D. S.; Butterfield, D. A.

    2006-12-01

    Uranium and Th concentration and isotopic composition of hydrothermal fluids at the Lost City Hydrothermal Field (LCHF) were determined using multi-collector inductively coupled plasma mass spectrometry (MC-ICP- MS). The LCHF is an off-axis, serpentinite-hosted hydrothermal system located at 30°N near the Mid- Atlantic Ridge. Carbonate chimneys reaching 60 m in height vent alkaline (pH~10), calcium-rich fluids at 40- 91°C and the towers are home to dense microbial communities. Vent fluid and seawater U and Th concentration and isotopic composition data provide critical information for constraining U-Th chimney ages. The increased sensitivity (1-2%) of MC-ICP-MS combined with an Aridus nebulization system allows the precise measurement of small quantities of sample (~150 ml) with low concentrations (<<1ng/g) of U and Th. In this study, we have developed MC-ICP-MS techniques to measure the U and Th concentration and isotopic composition (234U, 238U, 230Th, and 232Th) of eight hydrothermal fluid samples. Endmember fluids with ~1mmol/kg Mg have ~0.02 ng/g U, confirming that end-member fluids contain near-zero values of both Mg and U. Thorium concentrations of fluids are close to deep seawater values. U and Th isotopic compositions are reported at the permil level. These data may provide new insights into the role of serpentinite-hosted hydrothermal systems in the budgets of U and Th in the ocean. Techniques presented in this study may be applied to other hydrothermal and seep environments.

  13. Mineralogy and Oxygen Isotope Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende

    NASA Technical Reports Server (NTRS)

    Keller, L. P.; Snead, C.; Rahman, Z.; McKeegan, K. D.

    2012-01-01

    Hibonite-rich Ca- and Al-rich inclusions (CAIs) are among the earliest formed solids that condensed in the early nebula. We discovered an unusual refractory inclusion from the Allende CV3 chondrite (SHAL) containing an approx 500 micron long single crystal of hibonite and co-existing coarse-grained perovskite. The mineralogy and petrography of SHAL show strong similarities to some FUN inclusions, especially HAL. Here we report on the mineralogy, petrography, mineral chemistry and oxygen isotopic compositions in SHAL.

  14. In-Situ Oxygen Isotopic Composition of Tagish Lake: An Ungrouped Type 2 Carbonaceous Chondrite

    NASA Technical Reports Server (NTRS)

    Zolensky, Michael E.; Engrand, Cecile; Gounelle, Matthieu; Zolensky, Mike E.

    2001-01-01

    We have measured the oxygen isotopic composition of several components of Tagish Lake by ion microprobe. This meteorite constitutes the best preserved sample of C2 matter presently available for study. It presents two different lithologies (carbonate-poor and -rich) which have fairly comparable oxygen isotopic composition, with regard to both the primary or secondary minerals. For the olivine and pyroxene grains, their delta O-18 values range from - 10.5% to + 7.4% in the carbonate-poor lithology, with a mean Delta O-17 value of - 3.7 2.4%. In the carbonate-rich lithology, delta O-18 varies from - 7.9% to + 3.3%, and the mean Delta O-17 value is - 4.7 +/- 1.4%. Olivine inclusions (Fo(sub >99)) with extreme O-16-enrichment were found in both lithologies: delta O-18 = - 46.1 %, delta O-187= - 48.3% and delta O-18 = - 40.6%, delta O-17 = - 41.2% in the carbonate-rich lithology; delta O-18 = - 41.5%, delta O-17 = -43.4%0 in the carbonate-poor lithology. Anhydrous minerals in the carbonate-poor lithology are slightly more O-16-rich than in the carbonate-rich one. Four low-iron manganese-rich (LIME) olivine grains do not have an oxygen isotopic composition distinct from the other "normal" olivines. The phyllosilicate matrix presents the same range of oxygen isotopic compositions in both lithologies: delta O-18 from approximately 11 % to approximately 6%, with an average Delta. O-17 approximately 0%. Because the bulk Tagish Lake oxygen isotopic composition given by Brown et al. is on the high end of our matrix analyses, we assume that this "bulk Tagish Lake" composition probably only represents that of the carbonate-rich lithology. Calcium carbonates have delta O-18 values up to 35%, with Delta O-17 approximately 0.5%0. Magnetite grains present very high Delta O-17 values approximately + 3.4%0 +/- 1.2%. Given our analytical uncertainties and our limited carbonate data, the matrix and the carbonate seem to have formed in isotopic equilibrium. In that case, their large

  15. Secular changes in the oxygen isotopic composition of Devonian biogenic apatite

    NASA Astrophysics Data System (ADS)

    Breisig, S.; Joachimski, M. M.; Buggisch, W.

    2003-04-01

    Oxygen isotopes are a key tool for quantifying temperature and salinity of ancient sea water. Initially, pristine skeletal carbonates (preferentially LMC) have been utilized to monitor variations in the oxygen isotopic composition of past oceans. A high preservation potential of the primordial isotopic signature may also be awarded to conodonts. These microfossils consist of fluor-apatite (francolite) with a dense microcrystalline structure and therefore are comparatively insensitive with regard to diagenetic overprinting. Because conodonts are frequent in Devonian rocks and widely used as index fossils, their application for oxygen isotope analysis is espe-cially promising for this specific geological time interval. Laser-based microsampling or high-temperature combustion techniques (TC/EA) allows us to analyse microsamples of conodont apatite (0.5 to 1 mg). The oxygen isotope measurements are performed on trisilverphosphate after dissolving conodont apatite (0.5 to 1 mg) in nitric acid and precipitating the phosphate group as Ag_3PO_4. Conodont samples from different locations in Germany (Rheinisches Schieferge-birge) and the Czech Republic (Prague Basin) as well as from the United States (Iowa) and Morocco (Anti-Atlas) have been analysed. δ18Oapatite values are presented for the Lochkovian, Middle and Late Devonian. δ18Oapatite values for the Lochkovian (Prague Basin) vary between 18.5 and 19.0 ppm (δ18Oapatite values given in V-SMOW). Assuming an oxygen isotopic composition for Devonian seawater of -1 ppm (ice-free world), the δ18Oapatite values translate into tem-peratures of 26^o to 28^oC for the tropical Lochkovian ocean. Eifelian to Givetian conodonts (Rheinisches Schiefergebirge, Prague Basin) show δ18Oapatite values from 18.5 to 20.4 ppm, corresponding to paleotemperatures of 20 to 28^o C. The Middle to Late Devonian transition is mainly documented by conodonts from Iowa with δ18Oapatite values of 18 to 20 ppm (21-30^o C). Conodont δ18Oapatite

  16. Tungsten isotopic compositions of iron meteorites: Chronological constraints vs. cosmogenic effects

    NASA Astrophysics Data System (ADS)

    Markowski, A.; Quitté, G.; Halliday, A. N.; Kleine, T.

    2006-02-01

    High-precision W isotopic compositions are presented for 35 iron meteorites from 7 magmatic groups (IC, IIAB, IID, IIIAB, IIIF, IVA, and IVB) and 3 non-magmatic groups (IAB, IIICD, and IIE). Small but resolvable isotopic variations are present both within and between iron meteorite groups. Variations in the 182W/ 184W ratio reflect either time intervals of metal-silicate differentiation, or result from the burnout of W isotopes caused by a prolonged exposure to galactic cosmic rays. Calculated apparent time spans for some groups of magmatic iron meteorites correspond to 8.5 ± 2.1 My (IID), 5.1 ± 2.3 My (IIAB), and 5.3 ± 1.3 My (IVB). These time intervals are significantly longer than those predicated from models of planetesimal accretion. It is shown that cosmogenic effects can account for a large part of the W isotopic variation. No simple relationship exists with exposure ages, compromising any reliable method of correction. After allowance for maximum possible cosmogenic effects, it is found that there is no evidence that any of the magmatic iron meteorites studied here have initial W isotopic compositions that differ from those of Allende CAIs [ ɛ182W = - 3.47 ± 0.20; [T. Kleine, K. Mezger, H. Palme, E. Scherer and C. Münker, Early core formation in asteroids and late accretion of chondrite parent bodies: evidence from 182Hf- 182W in CAIs, metal-rich chondrites and iron meteorites, Geochim. Cosmochim. Acta (in press)]. Cosmogenic corrections cannot yet be made with sufficient accuracy to obtain highly precise ages for iron meteorites. Some of the corrected ages nevertheless require extremely early metal-silicate segregation no later than 1 My after formation of CAIs. Therefore, magmatic iron meteorites appear to provide the best examples yet identified of material derived from the first planetesimals that grew by runaway growth, as modelled in dynamic simulations. Non-magmatic iron meteorites have a more radiogenic W isotopic composition than magmatic

  17. Investigating the source, transport, and isotope composition of water vapor in the planetary boundary layer

    NASA Astrophysics Data System (ADS)

    Griffis, Timothy J.; Wood, Jeffrey D.; Baker, John M.; Lee, Xuhui; Xiao, Ke; Chen, Zichong; Welp, Lisa R.; Schultz, Natalie M.; Gorski, Galen; Chen, Ming; Nieber, John

    2016-04-01

    Increasing atmospheric humidity and convective precipitation over land provide evidence of intensification of the hydrologic cycle - an expected response to surface warming. The extent to which terrestrial ecosystems modulate these hydrologic factors is important to understand feedbacks in the climate system. We measured the oxygen and hydrogen isotope composition of water vapor at a very tall tower (185 m) in the upper Midwest, United States, to diagnose the sources, transport, and fractionation of water vapor in the planetary boundary layer (PBL) over a 3-year period (2010 to 2012). These measurements represent the first set of annual water vapor isotope observations for this region. Several simple isotope models and cross-wavelet analyses were used to assess the importance of the Rayleigh distillation process, evaporation, and PBL entrainment processes on the isotope composition of water vapor. The vapor isotope composition at this tall tower site showed a large seasonal amplitude (mean monthly δ18Ov ranged from -40.2 to -15.9 ‰ and δ2Hv ranged from -278.7 to -113.0 ‰) and followed the familiar Rayleigh distillation relation with water vapor mixing ratio when considering the entire hourly data set. However, this relation was strongly modulated by evaporation and PBL entrainment processes at timescales ranging from hours to several days. The wavelet coherence spectra indicate that the oxygen isotope ratio and the deuterium excess (dv) of water vapor are sensitive to synoptic and PBL processes. According to the phase of the coherence analyses, we show that evaporation often leads changes in dv, confirming that it is a potential tracer of regional evaporation. Isotope mixing models indicate that on average about 31 % of the growing season PBL water vapor is derived from regional evaporation. However, isoforcing calculations and mixing model analyses for high PBL water vapor mixing ratio events ( > 25 mmol mol-1) indicate that regional evaporation can account

  18. Investigating the source, transport, and isotope composition of water vapor in the planetary boundary layer

    SciTech Connect

    Griffis, Timothy J.; Wood, Jeffrey D.; Baker, John M.; Lee, Xuhui; Xiao, Ke; Chen, Zichong; Welp, Lisa R.; Schultz, Natalie M.; Gorski, Galen; Chen, Ming; Nieber, John

    2016-01-01

    Increasing atmospheric humidity and convective precipitation over land provide evidence of intensification of the hydrologic cycle – an expected response to surface warming. The extent to which terrestrial ecosystems modulate these hydrologic factors is important to understand feedbacks in the climate system. We measured the oxygen and hydrogen isotope composition of water vapor at a very tall tower (185 m) in the upper Midwest, United States, to diagnose the sources, transport, and fractionation of water vapor in the planetary boundary layer (PBL) over a 3-year period (2010 to 2012). These measurements represent the first set of annual water vapor isotope observations for this region. Several simple isotope models and cross-wavelet analyses were used to assess the importance of the Rayleigh distillation process, evaporation, and PBL entrainment processes on the isotope composition of water vapor. The vapor isotope composition at this tall tower site showed a large seasonal amplitude (mean monthly δ18Ov ranged from −40.2 to −15.9 ‰ and δ2Hv ranged from −278.7 to −113.0 ‰) and followed the familiar Rayleigh distillation relation with water vapor mixing ratio when considering the entire hourly data set. However, this relation was strongly modulated by evaporation and PBL entrainment processes at timescales ranging from hours to several days. The wavelet coherence spectra indicate that the oxygen isotope ratio and the deuterium excess (dv) of water vapor are sensitive to synoptic and PBL processes. According to the phase of the coherence analyses, we show that evaporation often leads changes in dv, confirming that it is a potential tracer of regional evaporation. Isotope mixing models indicate that on average about 31 % of the growing season PBL water vapor is derived from regional evaporation. However, isoforcing calculations and mixing model

  19. Isotopic Composition of Natural Nitrate in Groundwater in Los Alamos, New Mexico, USA

    NASA Astrophysics Data System (ADS)

    Chrystal, A. E.; Heikoop, J. M.; Longmire, P.; Dale, M.; Larson, T. E.; Perkins, G.; Fabyrka-Martin, J.; Simmons, A. M.; Fessenden-Rahn, J.

    2009-12-01

    Los Alamos National Laboratory (LANL) has established background concentrations for various dissolved constituents in local groundwater from perched-intermediate and regional aquifers in the vicinity of Los Alamos in north-central New Mexico. Typical background concentrations of nitrate (NO3-) are on the order of 0.31 mg/L as N (0.02 mM/L). In addition to natural sources, anthropogenic sources of NO3- in local groundwaters include industrial and treated sewage discharges released from LANL facilities, and treated sewage effluent discharges from Los Alamos County. We are using stable isotopes of nitrogen and oxygen in NO3- to distinguish among these sources, define groundwater flow paths, and evaluate groundwater mixing. Following the approach of McMahon and Böhlke (2006), we have explored the δ18O[NO3-] of water samples taken from background wells and springs in the Los Alamos area. NO3- from a spring and a well located in the Valles caldera, upgradient and upwind (relative to prevailing winds) of Los Alamos has δ15N and δ18O values of approximately 4.8 ‰ and -2.6 ‰, respectively. Tritium and unadjusted radiocarbon analyses indicate that these caldera waters predate LANL operations commencing in 1943. NO3- from groundwater locations in Los Alamos that exhibit background conditions has isotopic values similar to those of the caldera groundwater. Because local groundwater is relatively oxidizing, denitrification is not expected to be a factor in altering isotopic compositions of NO3-. Results indicate that there is little direct atmospheric contribution to dissolved NO3-, and that most NO3- is derived from bacterial nitrification in which one oxygen atom comes from atmospheric oxygen and two oxygen atoms come from soil porewater. Oxygen isotope values plot slightly below the expected isotopic trend for a 1:2 mix of these two sources, indicating either slight fractionation of oxygen isotopes during nitrification, or potential mixing with geological sources of

  20. Understanding climatic controls on Svalbard water vapour and precipitation isotopic composition

    NASA Astrophysics Data System (ADS)

    Masson-Delmotte, Valérie; Steen-Larsen, Hans-Christian; Zanetti, Nathalie; Cattani, Olivier; Maturilli, Marion; Debatin, Siegrid; Terzer, Stefan; Bonne, Jean-Louis; Schneider, Matthias

    2015-04-01

    We investigate the meteorological and climatic controls on the isotopic composition of vapour and precipitation at Ny Alesund, Svalbard. This is based on the IAEA database of monthly precipitation isotopic composition data spanning 1993-2012 as well as new measurements performed using a PICARRO CRDS analyzer deployed since June 2014 at Ny Alesund. The precipitation data depict a strong decoupling between oxygen 18 and temperature at the seasonal scale and for monthly anomalies. While a relationship is observed between winter precipitation isotopic composition and temperature, this disappears during summer, at the inter-annual scale. Moreover, the deuterium versus oxygen 18 relationship depicts different meteoric water lines in winter and summer, consistent with the strong seasonal cycle of deuterium excess, and indicating shifts in moisture origin. The continuous water vapour data (investigated from July to December 2014 so far) show in contrast a tight relationship between hourly oxygen 18 data and surface temperature and humidity, as well as strong antiphase between deuterium excess and oxygen 18. No significant diurnal variability is observed. We show how precipitation intermittency strongly alters the sampling provided by precipitation data and distorts the relationship with local temperature. The surface vapour deuterium data are compared with FTIR retrievals. The importance of changes in air mass origins is also assessed by comparison with moisture backtrajectories.

  1. Estimation of evaporative loss based on the stable isotope composition of water using Hydrocalculator

    NASA Astrophysics Data System (ADS)

    Skrzypek, Grzegorz; Mydłowski, Adam; Dogramaci, Shawan; Hedley, Paul; Gibson, John J.; Grierson, Pauline F.

    2015-04-01

    Accurate quantification of evaporative losses to the atmosphere from surface water bodies is essential for calibration and validation of hydrological models, particularly in remote arid and semi-arid regions, where intermittent rivers are generally minimally gauged. Analyses of the stable hydrogen and oxygen isotope composition of water can be used to estimate evaporative losses from individual pools in such regions in the absence of instrumental data but calculations can be complex, especially in highly variable systems. In this study, we reviewed and combined the most recent equations required for estimation of evaporative losses based on the revised Craig-Gordon model. The updated procedure is presented step-by-step, increasing ease of replication of all calculations. The main constraints and sources of uncertainties in the model were also evaluated. Based on this procedure we have designed a new software, Hydrocalculator, that allows quick and robust estimation of evaporative losses based on isotopic composition of water. The software was validated against measures of field pan evaporation under arid conditions in northwest Australia as well as published data from other regions. We found that the major factor contributing to the overall uncertainty in evaporative loss calculations using this method is uncertainty in estimation of the isotope composition of ambient air moisture.

  2. Boron isotopic composition of tourmaline from massive sulfide deposits and tourmalinites

    USGS Publications Warehouse

    Palmer, M.R.; Slack, J.F.

    1989-01-01

    Boron isotope ratios (11B/10B) have been measured on 60 tourmaline separates from over 40 massive sulfide deposits and tourmalinites from a variety of geologic and tectonic settings. The coverage of these localities is global (5 continents) and includes the giant ore bodies at Kidd Creek and Sullivan (Canada), Broken Hill (Australia), and Ducktown (USA). Overall, the tourmalines display a wide range in ??11B values from -22.8 to +18.3??? Possible controls over the boron isotopic composition of the tourmalines include: 1) composition of the boron source, 2) regional metamorphism, 3) water/rock ratios, 4) seawater entrainment, 5) temperature of formation, and 6) secular variations in seawater ??11B. The most significant control appears to be the composition of the boron source, particularly the nature of footwall lithologies; variations in water/ rock ratios and seawater entrainment are of secondary importance. The boron isotope values seem especially sensitive to the presence of evaporites (marine and non-marine) and carbonates in source rocks to the massive sulfide deposits and tourmalinites. ?? 1989 Springer-Verlag.

  3. Variations in the O-isotope composition of gas during the formation of chondrules from the CR chondrites

    NASA Astrophysics Data System (ADS)

    Schrader, Devin L.; Nagashima, Kazuhide; Krot, Alexander N.; Ogliore, Ryan C.; Hellebrand, Eric

    2014-05-01

    To better understand the environment of chondrule formation and constrain the O-isotope composition of the ambient gas in the Renazzo-like carbonaceous (CR) chondrite chondrule-forming region, we studied the mineralogy, petrology, and in situ O-isotope compositions of olivine in 11 barred olivine (BO) chondrules and pyroxene and silica in three type I porphyritic chondrules from the CR chondrites Gao-Guenie (b), Graves Nunataks (GRA) 95229, Pecora Escarpment (PCA) 91082, and Shişr 033. BO chondrules experienced a higher degree of melting than porphyritic chondrules, and therefore, it has been hypothesized that they more accurately recorded the O-isotope composition of the gas in chondrule-forming regions. We studied the O-isotope composition of silica as it has been hypothesized to have formed via direct condensation from the gas.

  4. Composition of Hydrothermal Vent Microbial Communities as Revealed by Analyses of Signature Lipids, Stable Carbon Isotopes and Aquificales Cultures

    NASA Technical Reports Server (NTRS)

    Jahnke, L. L.; Eder, W.; Huber, Robert; Hinrichs, K-U.; Hayes, J. M.; DesMarais, D. J.; Cady, S. L.; Hope, J. M.; Summons, R. E.

    2001-01-01

    This paper describes a study of lipid biomarker composition and carbon isotopic fractionation in cultured Aquificales and natural analogues from Yellowstone National Park. Additional information is contained in the original extended abstract.

  5. Oxygen - Osmium Isotopic Compositions of West Maui Lavas and the Link to Oceanic Lithosphere

    NASA Astrophysics Data System (ADS)

    Gaffney, A. M.; Nelson, B. K.; Reisberg, L.; Eiler, J. M.

    2003-12-01

    We use stratigraphically-controlled sequences of late shield-stage lavas from West Maui to investigate age-dependence and fine-scale complexity of chemical variation within this Kea-type Hawaiian volcano. With new O and Os isotope data we identify unique geochemical signals indicative of complex processes of mixing among source components. In W. Maui lavas, δ 18O and 187Os/188Os range from 4.5 to 5.2 and 0.1316 to 0.1394, respectively. One sample (187Os/188Os =0.158) has very low [Os] (20 ppt) and likely has been severely contaminated by shallow oceanic crust. These compositions, as well as 87Sr/86Sr (0.7034-0.7037) and 206Pb/204Pb (18.36-18.54), are typical of shield-stage lavas from other Kea-type volcanoes. Some W. Maui compositional variability correlates with stratigraphic height. All shallow samples have 187Os/188Os>=0.1333, and all deep samples have 187Os/188Os<=0.1330. The deep samples show a negative 187Os/188Os - 87Sr/86Sr correlation, but the shallow samples show no Os - Sr isotopic correlation. 187Os/188Os correlates with no other measured isotopic compositions except for δ 18O, for which the deep and shallow samples define two sub-parallel inversely correlated trends. δ 18O shows no other correlation with stratigraphy or other measured isotopic tracers. The inverse O-Os isotopic correlation of W. Maui is distinct from that observed for other Hawaiian volcanoes (e.g. Mauna Kea, Koolau) or within the Hawaiian suite as a whole. Age-dependent sampling of at least three components is required to describe the O-Os-Sr isotopic variation we observe at W. Maui. Similar intra-volcano correlation in 87Sr/86Sr - 206Pb/204Pb - trace element compositions is consistent with mixing of small-degree partial melts of gabbroic oceanic crust with plume-derived Kea-type magmas. We infer that this gabbroic endmemember is characterized by δ 18O < 4.5 and 187Os/188Os > 0.133. The remainder of the variability is the result of short-lived chemical heterogeneities in the Kea

  6. The Triple Oxygen Isotopic Composition of High 3He/4He Mantle

    NASA Astrophysics Data System (ADS)

    Jackson, C.; Parman, S. W.; Starkey, N.; Greenwood, R.; Franchi, I.; Jackson, M. G.; Fitton, J. G.; Stewart, F. M.; Larsen, L. M.

    2015-12-01

    Measurements of Xe isotope ratios in ocean island basalts (OIB) suggest that Earth's mantle accreted heterogeneously, and that compositional remnants of accretion are sampled by modern, high-3He/4He OIB associated with the Icelandic and Samoan plumes [1]. If so, the high-3He/4He source may also have a distinct oxygen isotopic composition from the rest of the mantle. Here, we test if the major elements of the high-3He/4He source preserve any evidence of heterogeneous accretion using measurements of three oxygen isotopes on olivine from a variety of high-3He/4He OIB locations. To high precision, the ∆17O value of high-3He/4He olivines from Hawaii, Pitcairn, Baffin Island and Samoa, are indistinguishable from bulk mantle olivine (Δ17OBulk Mantle - Δ17OHigh 3He/4He olivine = -0.002 ± 0.004 (2 x SEM) ‰). Thus, there is no resolvable oxygen isotope evidence for heterogeneous accretion in the high-3He/4He source. Modelling of mixing processes indicates that if an early-forming, oxygen-isotope distinct mantle did exist, either the anomaly was extremely small, or the anomaly was homogenised away by later mantle convection. The δ18O values of olivine with the highest 3He/4He ratios from a variety of OIB locations have a relatively uniform composition (~5 ‰). This composition is intermediate to values associated with the depleted MORB mantle and the average mantle. Similarly, δ18O values of olivine from high-3He/4He OIB correlate with radiogenic isotope ratios of He, Sr, and Nd. Combined, this suggests that oxygen remains coupled to the more incompatible elements during melt production and migration and that the intermediate δ18O value is a feature of the mantle source. The processes responsible for the δ18O signature of high-3He/4He mantle are not certain, but δ18O-87Sr/86Sr correlations indicate that it may be connected to a predominance of a HIMU-like (high U/Pb) component or other moderate δ18O components recycled into the high-3He/4He source. [1] S

  7. Triple oxygen isotopic composition of the high-3He/4He mantle

    NASA Astrophysics Data System (ADS)

    Starkey, N. A.; Jackson, C. R. M.; Greenwood, R. C.; Parman, S.; Franchi, I. A.; Jackson, M.; Fitton, J. G.; Stuart, F. M.; Kurz, M.; Larsen, L. M.

    2016-03-01

    Measurements of Xe isotope ratios in ocean island basalts (OIB) suggest that Earth's mantle accreted heterogeneously, and that compositional remnants of accretion are sampled by modern, high-3He/4He OIB associated with the Icelandic and Samoan plumes. If so, the high-3He/4He source may also have a distinct oxygen isotopic composition from the rest of the mantle. Here, we test if the major elements of the high-3He/4He source preserve any evidence of heterogeneous accretion using measurements of three oxygen isotopes on olivine from a variety of high-3He/4He OIB locations. To high precision, the Δ17O value of high-3He/4He olivines from Hawaii, Pitcairn, Baffin Island and Samoa, are indistinguishable from bulk mantle olivine (Δ17OBulk Mantle - Δ17OHigh 3He/4He olivine = -0.002 ± 0.004 (2 × SEM)‰). Thus, there is no resolvable oxygen isotope evidence for heterogeneous accretion in the high-3He/4He source. Modelling of mixing processes indicates that if an early-forming, oxygen-isotope distinct mantle did exist, either the anomaly was extremely small, or the anomaly was homogenised away by later mantle convection. The δ18O values of olivine with the highest 3He/4He ratios from a variety of OIB locations have a relatively uniform composition (∼5‰). This composition is intermediate to values associated with the depleted MORB mantle and the average mantle. Similarly, δ18O values of olivine from high-3He/4He OIB correlate with radiogenic isotope ratios of He, Sr, and Nd. Combined, this suggests that magmatic oxygen is sourced from the same mantle as other, more incompatible elements and that the intermediate δ18O value is a feature of the high-3He/4He mantle source. The processes responsible for the δ18O signature of high-3He/4He mantle are not certain, but δ18O-87Sr/86Sr correlations indicate that it may be connected to a predominance of a HIMU-like (high U/Pb) component or other moderate δ18O components recycled into the high-3He/4He source.

  8. s-process Ba isotopic compositions in presolar SiC from the Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Prombo, C. A.; Podosek, F. A.; Amari, S.; Lewis, R. S.

    1993-01-01

    We have measured, by thermal ionization mass spectrometry, the isotopic composition of Ba in interstellar SiC-enriched samples (the KJ series) prepared from the Murchison meteorite. Ba in these samples is strongly enriched in components plausibly understood as s-process nucleosynthetic products. Inferred s-process compositions are different from the average s-process contribution to solar system materials in the sense of indicating lower effective neutron exposure. There are variations in s-process compositions which correlate with grain size, indicating lower neutron exposure for the larger grains. The inferred s-process compositions differ significantly from previous theoretical predictions, indicating the need for revision of relevant neutron capture cross sections and providing a target for more detailed modeling of s-process nucleosynthesis in specific stellar environments.

  9. Natural Ca Isotope Composition of Urine as a Rapid Measure of Bone Mineral Balance

    NASA Astrophysics Data System (ADS)

    Skulan, J.; Gordon, G. W.; Morgan, J.; Romaniello, S. J.; Smith, S. M.; Anbar, A. D.

    2011-12-01

    Naturally occurring stable Ca isotope variations in urine are emerging as a powerful tool to detect changes in bone mineral balance. Bone formation depletes soft tissue of light Ca isotopes while bone resorption releases isotopically light Ca into soft tissue. Previously published work found that variations in Ca isotope composition could be detected at 4 weeks of bed rest in a 90-day bed rest study (data collected at 4, 8 and 12 weeks). A new 30-day bed rest study involved 12 patients on a controlled diet, monitored for 7 days prior to bed rest and 7 days post bed rest. Samples of urine, blood and food were collected throughout the study. Four times daily blood samples and per void urine samples were collected to monitor diurnal or high frequency variations. An improved chemical purification protocol, followed by measurement using multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS) allowed accurate and precise determinations of mass-dependent Ca isotope variations in these biological samples to better than ±0.2% (δ44/42Ca) on <25 μg of Ca. Results from this new study show that Ca isotope ratios shift in a direction consistent with net bone loss after just 7 days, long before detectible changes in bone density by X-ray measurements occur. Consistent with this interpretation, the Ca isotope variations track changes observed in N-teleopeptide, a bone resorption biomarker. Bone-specific alkaline phosphatase, a bone formation biomarker, is unchanged over this period. Ca isotopes can in principle be used to quantify net changes in bone mass. Using a mass-balance model, our results indicate an average loss of 0.62 ± 0.16 % in bone mass over the course of this 30-day study. This is consistent with the rate of bone loss in longer-term studies as seen by X-ray measurements. This Ca isotope technique should accelerate the pace of discovery of new treatments for bone disease and provide novel insights into the dynamics of bone metabolism.

  10. The triple oxygen isotope composition of leaf waters in Mpala, central Kenya

    NASA Astrophysics Data System (ADS)

    Li, S.; Levin, N.; Soderberg, K.; Dennis, K. J.; Caylor, K. K.

    2013-12-01

    The triple oxygen isotopic composition of water is an emerging tool for investigating the hydrological environment. The δ18O-δ17O relationship differs during kinetic and equilibrium isotope fractionation, such that the 17O depletion can be sensitive to relative humidity (Rh) during kinetic fractionation, mixing among different pools, and to the specific mode of kinetic fractionation. It has been proposed that the δ18O-δ17O relationship during evapotranspiration, as characterized by the slope λ(stem-leaf) on a ln(δ17O+1) vs. ln(δ18O+1) plot, is mainly controlled by Rh but not affected by other environmental conditions or by plant species. In order to understand the sensitivity of λ(stem-leaf) to Rh and the utility of 17O-excess (the deviation of δ17O from a reference slope) in the terrestrial biosphere as a tracer of Rh conditions today and in the past, this study expands the triple oxygen isotope measurements of leaf waters to additional species in a semiarid environment. Paired stem and leaf waters of Acacia and grasses were collected in the Mpala Research Center in central Kenya and analyzed for their triple oxygen isotope composition. Leaf waters that were sampled diurnally (8 sampling intervals between 6 am and 5 pm) exhibit a range in δ18O and 17O-excess values of 11.2‰ and 107 per meg respectively for Acacia brevispica, and 14.4‰ and 147 per meg for the grass Panicum maximum. Except for one sample collected at 7am, the λ(stem-leaf) values for grasses are systematically lower (0.0012 to 0.0110) than Acacia λ(stem-leaf) values at the corresponding time of day; this might be explained by the progressive evaporative isotopic enrichment and mixing processes of leaf water along parallel veins of grass leaves. Most of the triple oxygen isotope composition of the Acacia leaf waters can be predicted using Craig-Gordon model. We built a mass balance model of an evolving leaf water system from nonsteady-state to steady-state conditions during

  11. Probing the homogeneity of the isotopic composition and molar mass of the ‘Avogadro’-crystal

    NASA Astrophysics Data System (ADS)

    Pramann, Axel; Lee, Kyoung-Seok; Noordmann, Janine; Rienitz, Olaf

    2015-12-01

    Improved measurements on silicon crystal samples highly enriched in the 28Si isotope (known as ‘Si28’ or AVO28 crystal material) have been carried out at PTB to investigate local isotopic variations in the original crystal. This material was used for the determination of the Avogadro constant NA and therefore plays an important role in the upcoming redefinition of the SI units kilogram and mole, using fundamental constants. Subsamples of the original crystal have been extensively studied over the past few years at the National Research Council (NRC, Canada), the National Metrology Institute of Japan (NMIJ, Japan), the National Institute of Standards and Technology (NIST, USA), the National Institute of Metrology (NIM, People’s Republic of China), and multiple times at PTB. In this study, four to five discrete, but adjacent samples were taken from three distinct axial positions of the crystal to obtain a more systematic and comprehensive understanding of the distribution of the isotopic composition and molar mass throughout the crystal. Moreover, improved state-of-the-art techniques in the experimental measurements as well as the evaluation approach and the determination of the calibration factors were utilized. The average molar mass of the measured samples is M  =  27.976 970 12(12) g mol-1 with a relative combined uncertainty uc,rel(M)  =  4.4 ×10-9. This value is in astounding agreement with the values of single samples measured and published by NIST, NMIJ, and PTB. With respect to the associated uncertainties, no significant variations in the molar mass and the isotopic composition as a function of the sample position in the boule were observed and thus could not be traced back to an inherent property of the crystal. This means that the crystal is not only ‘homogeneous’ with respect to molar mass but also has predominantly homogeneous distribution of the three stable Si isotopes.

  12. Chemistry and oxygen isotopic composition of cluster chondrite clasts and their components in LL3 chondrites

    NASA Astrophysics Data System (ADS)

    Metzler, Knut; Pack, Andreas

    2016-02-01

    Cluster chondrites are characterized by close-fit textures of deformed and indented chondrules, taken as evidence for hot chondrule accretion (Metzler). We investigated seven cluster chondrite clasts from six brecciated LL3 chondrites and measured their bulk oxygen isotopic and chemical composition, including REE, Zr, and Hf. The same parameters were measured in situ on 93 chondrules and 4 interchondrule matrix areas. The CI-normalized REE patterns of the clasts are flat, showing LL-chondritic concentrations. The mean chemical compositions of chondrules in clasts and other LL chondrites are indistinguishable and we conclude that cluster chondrite chondrules are representative of the normal LL chondrule population. Type II chondrules are depleted in MgO, Al2O3 and refractory lithophiles (REE, Zr, Hf) by factors between 0.65 and 0.79 compared to type I chondrules. The chondrule REE patterns are basically flat with slight LREE < HREE fractionations. Many chondrules exhibit negative Eu anomalies while matrix shows a complementary pattern. Chondrules scatter along a correlation line with a slope of 0.63 in the oxygen 3-isotope diagram, interpreted as the result of O-isotope exchange between chondrule melts and 18O-rich nebular components. In one clast, a distinct anticorrelation between chondrule size and δ18O is found, which may indicate a more intense oxygen isotope exchange by smaller chondrules. In some clasts the δ18O values of type I chondrules are correlated with concentrations of SiO2 and MnO and anticorrelated with MgO, possibly due to the admixture of a SiO2- and MnO-rich component to chondrule melts during oxygen isotope exchange. Two chondrules with negative anomalies in Sm, Eu, and Yb were found and may relate their precursors to refractory material known from group III CAIs. Furthermore, three chondrules with strong LREE > HREE and Zr/Hf fractionations were detected, whose formation history remains to be explained.

  13. Oxygen isotope composition of evapotranspiration and its relation to C4 photosynthetic discrimination

    NASA Astrophysics Data System (ADS)

    Griffis, T. J.; Lee, X.; Baker, J. M.; Billmark, K.; Schultz, N.; Erickson, M.; Zhang, X.; Fassbinder, J.; Xiao, W.; Hu, N.

    2011-03-01

    The oxygen isotope of water (18O-H2O) and carbon dioxide (18O-CO2) is an important signal of global change and can provide constraints on the coupled carbon-water cycle. Here, simultaneous observations of 18O-H2O (liquid and vapor phases) and 18O-CO2 were used to investigate the relation between canopy leaf water 18O enrichment, 18O-CO2 photosynthetic discrimination (18Δ), isotope disequilibrium (Deq), and the biophysical factors that control their temporal variability in a C4 (Zea mays L.) ecosystem. Data and analyses are presented from a 74 day experiment conducted in Minnesota during summer 2009. Eddy covariance observations indicate that the oxygen isotope composition of C4 evapotranspiration (δE) ranged from about -20‰ (VSMOW scale) in the early morning to -5‰ after midday. These values were used to estimate the isotope composition at the sites of leaf water evaporation (δL,e) assuming non-steady-state conditions and revealed a strong diurnal pattern ranging from about -5‰ in the early morning to +10‰ after midday. With the addition of net ecosystem CO2 exchange measurements and carbonic anhydrase (CA) assays, we derived canopy-scale 18Δ. These estimates typically varied from 11.3 to 27.5‰ (VPDB scale) and were shown to vary significantly depending on the steady state or non-steady-state assumptions related to leaf water enrichment. We demonstrate that the impact of turbulence on kinetic fractionation and steady state assumptions result in larger estimates of 18Δ and Deq. Further, the results indicate that both leaf-scale and canopy-scale CO2 hydration efficiency may be substantially lower than that previously reported for laboratory conditions. These results may have important implications for interpreting variations in atmospheric 18O-CO2 and constraining regional carbon budgets based on the oxygen isotope tracer approach.

  14. Studies on stable isotopic composition of daily rainfall from Kozhikode, Kerala, India.

    PubMed

    Unnikrishnan Warrier, C; Praveen Babu, M; Sudheesh, M; Deshpande, Rajendrakumar D

    2016-06-01

    The stable isotopic compositions of all major daily rain fall samples (n = 113) collected from Kozhikode station in Kerala, India, for the year 2010 representing the pre-monsoon, southwest and northeast monsoon seasons are examined. The isotopic variations δ(18)O, δ(2)H and d-excess in daily rainfall ranged from δ(18)O: -4.4 to 2 ‰, δ(2)H: -25.3 to 13.8 ‰, and d-excess: -2.4 to 15.3 ‰; δ(18)O: -9.7 to -0.6 ‰, δ(2)H: -61.7 to 5.3 ‰, and d-excess 5.8 to 17.4 ‰; δ(18)O -11.3 to -1.4 ‰, δ(2)H: -75.3 to 0.9 ‰, and d-excess: 8.8 to 21.3 ‰ during the pre-, southwest and northeast monsoon periods, respectively. Thus, daily rainfall events during two monsoon periods had a distinct range of isotopic variations. The daily rain events within the two monsoon seasons also exhibited periodic variations. The isotopic composition of rain events during pre-monsoon and a few low-intensity events during the southwest monsoon period had imprints of secondary evaporation. This study analysing the stable isotopic characteristics of individual rain events in southern India, which is influenced by dual monsoon rainfall, will aid in a better understanding of its mechanism. PMID:26617222

  15. The bulk isotopic composition of hydrocarbons in subaerial volcanic-hydrothermal emissions from different tectonic settings

    NASA Astrophysics Data System (ADS)

    Fiebig, J.; Tassi, F.; Vaselli, O.; Viveiros, M. F.; Silva, C.; Lopez, T. M.; D'Alessandro, W.; Stefansson, A.

    2015-12-01

    Assuming that methane and its higher chain homologues derive from a common source, carbon isotope patterns have been applied as a criterion to identify occurrences of abiogenic hydrocarbons. Based on these, it has been postulated that abiogenic hydrocarbon production occurs within several (ultra)mafic environments. More evolved volcanic-hydrothermal systems may also provide all the prerequisites necessary for abiogenic hydrocarbon production, such as availability of inorganic CO2, hydrogen and heat. We have investigated the chemical and isotopic composition of n-alkanes contained within subaerial hydrothermal discharges emitted from a range of hot spot, subduction and rift-related volcanoes to determine the origin of hydrocarbons in these systems. Amongst these are Nisyros (Greece), Vesuvio, Campi Flegrei, Ischia, Pantelleria and Vulcano (all Italy), Mt. Mageik and Trident (USA), Copahue (Argentina), Teide (Spain), Furnas and Fogo (Portugal). The carbon isotopic composition of methane emitted from these sites varies from -65 to -8‰ , whereas δ13C of ethane and propane exhibit a much narrower variation from -17‰ to -31‰. Methane that occurs most enriched in 13C is also characterized by relatively positive δD values ranging up to -80‰. Carbon isotope reversals between methane and ethane are only observed for locations exhibiting δ13C-CH4 values > -20‰, such as Teide, Pantelleria, Trident and Furnas. At Furnas, δ13C-CH4 varies by 50‰ within a relatively short distance of <50m between two vents, whereas δ13C-C2H6 varies by less than 2‰ only. For some of the investigated locations apparent carbon isotopic temperatures between methane and CO2 are in agreement with those derived from gas concentration geothermometers. At these locations methane, however seems to be in disequilibrium with ethane and propane. These findings imply that methane on the one hand and the C2+ hydrocarbons on the other hand often might derive from distinct sources.

  16. The isotopic composition of uranium and lead in Allende inclusions and meteoritic phosphates

    NASA Technical Reports Server (NTRS)

    Chen, J. H.; Wasserburg, G. J.

    1981-01-01

    The isotopic compositions of uranium and lead in Ca-Al-rich inclusions from the Allende chondrite and in whitlockite from the St. Severin chondrite and the Angra dos Reis achondrite are reported. Isoptopic analysis of acid soluble fractions of the Allende inclusions and the meteoritic whitlockite, which show isotopic anomalies in other elements, reveals U-235/U-238 ratios from 1/137.6 to 1/138.3, within 20 per mil of normal terrestrial U abundances. The Pb isotopic compositions of five coarse-grained Allende inclusions give a mean Pb-207/Pb-206 model age of 4.559 + or - 0.015 AE, in agreement with the U results. Pb isotope ratios of two fine-grained inclusions and a coarse-grained inclusion with strong mass fractionation and some nonlinear isotopic anomalies indicate that the U-Pb systems of these inclusions have evolved differently from the rest of Allende. Th/U abundance ratios in the Allende inclusions and meteoritic phosphate are found to range from 3.8 to 96, presumably indicating an optimal case for Cm/U fractionation, although the normal U concentrations do not support claims of abundant live Cm-247 or Cm-247/U-238 fractionation at the time of meteorite formation, in contrast to previous results. A limiting Cm-247/U-235 ratio of 0.004 at the time of meteorite formation is calculated which implies that the last major r process contribution at the protosolar nebula was approximately 100 million years prior to Al-26 formation and injection.

  17. Magnesium isotopic compositions of altered oceanic basalts and gabbros from IODP site 1256 at the East Pacific Rise

    NASA Astrophysics Data System (ADS)

    Huang, Jian; Ke, Shan; Gao, Yongjun; Xiao, Yilin; Li, Shuguang

    2015-08-01

    To investigate the behaviour of Mg isotopes during alteration of oceanic crust and constrain the Mg isotopic compositions of the altered oceanic crust (AOC), high-precision Mg isotope analyses have been conducted on forty-four altered basalts and gabbros recovered from IODP site 1256, which represent the carbonate-barren AOC formed at the East Pacific Rise (EPR). These samples were altered by interaction of seawater-derived fluids with oceanic crust at different temperatures and water/rock ratios. With the exception of one sample that has a slightly heavier Mg isotopic composition (δ26Mg = 0.01 ± 0.08‰), all the other samples have relatively homogenous and mantle-like Mg isotopic compositions, with δ26Mg ranging from - 0.36 to - 0.14‰ (an average value of - 0.25 ± 0.11‰, 2SD, n = 43). This suggests that limited Mg isotope fractionation occurred during alteration of oceanic crust at the EPR at bulk rock scale, irrespective of highly variable alteration temperatures and variable water/rock ratios. Thus, our study suggests that the offset of δ26Mg values between seawater and global runoff dominantly results from the formation of marine dolomite as a sink for Mg. The mantle-like Mg isotopic composition further indicates that recycling of carbonate-barren AOC would not result in Mg isotope heterogeneity of the mantle at global scale. Consequently, the light Mg isotopic compositions of the mantle at local scale must result from incorporation of recycled Mg isotopically light carbonates.

  18. Isotopic Composition of the Neolithic Alpine Iceman's Tooth Enamel and Clues to his Origin

    NASA Astrophysics Data System (ADS)

    Muller, W.; Muller, W.; Halliday, A. N.

    2001-12-01

    Five small enamel fragments from three teeth of the upper right jaw from the mummy of the Neolithic Alpine Iceman have been investigated for their isotopic composition in order to shed light on his geographic origins. Soils from approximately contemporaneous sites were sampled for comparison. Tooth enamel forms ontogenetically very early and is not re-mineralized during later lifetime (unlike with bone material). Therefore, unique insights into the Iceman's childhood can be acquired. Enamel also is the densest tissue of a human body and is thus less susceptible to post-mortem alteration. Both radiogenic (Sr, Pb, Nd) and stable isotopes (O, C) are investigated. Radiogenic isotopes allow reconstruction of the local geological background, because humans incorporate Sr, Pb and Nd from their local environment by eating local food. Stable isotopes provide information about altitude and/or position relative to the main Alpine watershed. High spatial-resolution laser-ablation ICPMS profiles reveal that most elements are distributed in a manner that is essentially similar to modern human teeth except of that La, Ce, Nd (LREE) show up to a 100-fold enrichment towards the outer enamel surface. These uptake-profiles may reflect interaction with melt water, consistent with data for the composition of samples of the Iceman's skin. Biogenic apatites (enamel, bone) have very low in-vivo LREE concentrations, but take up LREEs post-mortem from the burial environment. Ice core samples from the finding site show concentrations up to 400 ppt Ce. Such high uptake of the LREEs precludes the derivation of an in-vivo Nd isotopic signal, but both other radiogenic tracers, Sr and Pb, show pristine (in-vivo) concentrations of 87 ppm and 0.1 ppm, respectively. Strontium isotopic compositions were determined on fragments from the canine, the first and second premolar (1 - 9 mg) and two hip bone samples, utilizing three sequential leaching steps for each sample to detect possible alteration

  19. Chemical and isotope compositions of nitric thermal water of Baikal rift zone

    NASA Astrophysics Data System (ADS)

    Plyusnin, A. M.; Chernyavsky, M. K.; Peryazeva, E. G.

    2010-05-01

    Three types of hydrotherms (nitric, carbonaceous and methane) are distinguished within the Baikal Rift Zone. The unloading sites of nitric therms are mostly located in the central and north-eastern parts of the Rift. Several chemical types are found among nitric therms (Pinneker, Pisarsky, Lomonosov, 1968; Lomonosov, 1974, etc.). The formation of terms being various in chemical compositions is associated with effect of several factors, i.e. various chemical, mineralogical compositions of rocks, various temperatures, extent of interaction in water-rock system, etc. The ratio data of water oxygen and hydrogen isotopes of the studied thermal springs indicate that water is largely of meteoric origin. All established ratios of oxygen (δ18OSMOW = -19.5‰ - -17.5‰) and hydrogen (δDSMOW = -155‰ - - 130‰) isotopes are along the line of meteoric waters. Oxygen values from -20‰ to -5‰ are characteristic of the current meteoric and surface waters in the region. The average value equals -16.5‰ in Lake Baikal. By our data, a large group with oxygen lighter isotope composition that corresponds to isotope ratio being specific for glaciers is revealed in fissure-vein waters. Significant shift toward the oxygen getting heavier is observed in some springs. It is mostly observed in the springs that form chemical composition within the area of the intrusive and metamorphic rock distribution. As a result of hydrolysis reaction of alumosilicates, heavy isotope passes from rocks into water molecule, whereas oxygen heavy isotope passes from rocks into solutes during decomposition of carbonates. High contents of fluoride and sulfate-ions are specific feature of the Baikal Rift Zone most nitric therms. Water is tapped in one of the drill holes, where fluoride-ion dominates in its anion composition (46.7 mg/dm3) and pH reaches 10, 12. The sulphate sulphur isotope composition studies carried out allow to conclude that its heavy isotope (δ34SCDT = +25‰ - +30‰) prevails in

  20. Correction of NPL-2013 estimate of the Boltzmann constant for argon isotopic composition and thermal conductivity

    NASA Astrophysics Data System (ADS)

    de Podesta, Michael; Yang, Inseok; Mark, Darren F.; Underwood, Robin; Sutton, Gavin; Machin, Graham

    2015-10-01

    In 2013, a team from NPL, Cranfield University and SUERC published an estimate of the Boltzmann constant based on precision measurements of the speed of sound in argon. A key component of our results was an estimate of the molar mass of the argon gas used in our measurements. To achieve this we made precision comparison measurements of the isotope ratios found in our experimental argon against the ratios of argon isotopes found in atmospheric air. We then used a previous measurement of the atmospheric argon isotope ratios to calibrate the relative sensitivity of the mass spectrometer to different argon isotopes. The previous measurement of the atmospheric argon isotope ratios was carried out at KRISS using a mass spectrometer calibrated using argon samples of known isotopic composition, which had been prepared gravimetrically. We report here a new measurement made at KRISS in October 2014, which directly compared a sample of our experimental gas against the same gravimetrically-prepared argon samples. We consider that this direct comparison has to take precedence over our previous more indirect comparison. This measurement implies a molar mass which is 2.73(60) parts in 106 lighter than our 2013 estimate, a shift which is seven times our 2013 estimate of the uncertainty in the molar mass. In this paper we review the procedures used in our 2013 estimate of molar mass; describe the 2014 measurement; highlight some questions raised by the large change in our estimate of molar mass; and describe how we intend to address the inconsistencies between them. We also consider the effect of a new estimate of the low pressure thermal conductivity of argon at 273.16 K. Finally we report our new best estimate of the Boltzmann constant with revised uncertainty, taking account of the new estimates for the molar mass and the thermal conductivity of the argon.

  1. Discrimination of the Cigarettes Geographical Origin by DRC-ICP-MS Measurements of Pb Isotope Compositions

    NASA Astrophysics Data System (ADS)

    Guo, W.; Hu, S.; Jin, L.

    2014-12-01

    Trace Pb are taken up with the same isotopic ratios as is present in the source soil, and the isotopic composition of Pb could used to reflect these sources and provide powerful indicators of the geographic origin of agriculture products derived from vegetative matter. We developed a simple and high throughput method, which based on DRC-ICP-MS for determination of Pb isotope ratios for discriminating the geographic origin of cigarettes. After acid digestion procedure, the cigarette digested solutions were directly analyzed by ICP-QMS with a DRC pressurized by the non-reactive gas Ne. In the DRC, Ne molecules collision with Pb ions and improves Pb isotope ratios precision 3-fold, which may be due to the collisional dampling smoothes out the ion beam fluctuations. Under the optimum DRC rejection parameter Q (RPq = 0.45), the main matrix components (K, Na, Ca, Mg, Al, Fe etc.) originating from cigarettes were filtered out. Mass discrimination of 208Pb/206Pb ratio in Ne DRC mode increased 0.3% compared to the standard mode, the mass bias due to the in-cell Ne gas collision can be accurately corrected by NIST 981 Pb isotope standard. This method was verified by a tobacco reference material CTV-OTL-2. Results of 208Pb/206Pb and 207Pb/206Pb were 2.0848 ± 0.0028 (2δ) and 0.8452 ± 0.0011 (2δ) for CTA-VTL-2, which were agreed with the literature values (208Pb/206Pb = 2.0884 ± 0.0090 and 207Pb/206Pb = 0.8442 ± 0.0032). The precision of Pb isotope ratios (208Pb/206Pb and 207Pb/206Pb) for the cigarette samples are ranged from 0.01 to 0.08% (N = 5). It has sufficient precision to discriminate 91 different brand cigarettes originated from four different geographic regions (Shown in Fig).

  2. The osmium isotopic composition of convecting upper mantle deduced from ophiolite chromites

    NASA Astrophysics Data System (ADS)

    Walker, Richard J.; Prichard, Hazel M.; Ishiwatari, Akira; Pimentel, Márcio

    2002-01-01

    Chromites separated from the upper mantle or lower crustal portions of 18 ophiolites ranging in age from 900 Ma to 50 Ma are examined for Re-Os isotopic systematics. The ophiolites include both MORB and back arc types, although most are from supra-subduction zone (SSZ) settings. The chromites are robust indicators of the initial Os isotopic compositions of the systems sampled. There is very limited range in calculated initial γ Os values, with the entire group averaging +1.31. Least squares linear regression of the age of chromite formation (in Ga) versus initial 187Os/ 188Os of a filtered suite yields a slope of -0.0058±0.0019 (2σ) and a present day intercept of 0.12809±0.00085 (2σ), equivalent to a γ Os value of +0.9±0.6. Of the suite of 51 samples analyzed, 68% lie within ±1% of this evolution trajectory. Although most of the samples formed in SSZ environments, there is little evidence to suggest modification of the mantle Os isotopic composition via radiogenic melts or fluids derived from subducting slabs. The ophiolite data are interpreted as representative of the convecting upper mantle and suggest that the present isotopic composition of the convecting upper mantle averages approximately 1.2% less radiogenic than the estimated minimum composition of the primitive upper mantle of 0.1296±8 (Meisel et al., 2001). The most likely explanation for the difference is the formation, subduction and isolation of some portion of the mafic oceanic crust. Using models based on the assumption that the convecting upper mantle comprises 50% of the total mass of the mantle, and that the average isolation period for subducted oceanic crust is 1.5 to 2.0 Ga, it is estimated that approximately 2 to 3% of the total mass of the mantle is composed of subducted mafic oceanic crust that remains isolated from the convecting upper mantle. Because the isotopic compositions of the DMM and PUM overlap within uncertainties, however, the results do not require any isolated slab

  3. The Nd isotopic composition of Adélie Coast Bottom Water - insights from GIPY6 cruise along 140°E

    NASA Astrophysics Data System (ADS)

    van de Flierdt, T.; Lambelet, M.; Butler, E. C. V.; Bowie, A. R.; Rintoul, S. R.; Watson, R. J.; Remenyi, T.; Lannuzel, D.

    2014-12-01

    Cold and dense Antarctic Bottom Water (AABW) is an important component of the global overturning circulation. The majority of AABW forms in three discrete locations around the Antarctic continent, the Weddell Sea (Atlantic sector of the Southern Ocean), the Ross Sea (Pacific sector), and the Adélie Depression (~142-145°E, ~66-67°S; Indian sector). Adélie Land Bottom Water (ALBW) is formed as dense shelf waters beneath coastal polynyas, and periodically overspills and is exported to the abyssal ocean. Previous work suggested that this particular water mass not only carries characteristic hydrographic properties, but that it may also carry a distinct radiogenic isotope composition, which would allow tracing local bottom water formation back in time.We here present new results for the Nd isotope composition and concentration of seawater collected during the GIPY6 voyage from Tasmania (Australia) to the Adélie Depression (Antarctica) (SR3 CASO-GEOTRACES transect; March-April 2008). A total of four seawater profiles were sampled at four depths each across the Southern Ocean (48 to 65.5°S) along the 140°E meridian. Seawater was filtered and acidified aboard the Aurora Australis, and analysed back in the home laboratory using pre-concentration on C18 cartridges, 2 stage ion chromatography and NdO+ analysis by TIMS. Results confirm a rather homogenous isotopic composition of Circumpolar Deep Waters (eNd = -8.2 to -9.0), but a distinct isotopic fingerprint of ALBW (eNd = -9.3 to -10.5). ALBW contributes up to 2 Sverdrup of AABW annually, and cold temperatures and relatively high oxygen and CFC-rich contents of this water mass correlate with rather negative Nd isotopic compositions. Absolute values are more than two epsilon units lower than the ones observed in Ross Sea bottom water, supporting the idea that the proximity of the old Adélie craton facilitates the formation of a particularly unradiogenic variety of AABW.

  4. Amino acid compositions in heated carbonaceous chondrites and their compound-specific nitrogen isotopic ratios

    NASA Astrophysics Data System (ADS)

    Chan, Queenie Hoi Shan; Chikaraishi, Yoshito; Takano, Yoshinori; Ogawa, Nanako O.; Ohkouchi, Naohiko

    2016-01-01

    A novel method has been developed for compound-specific nitrogen isotope compositions with an achiral column which was previously shown to offer high precision for nitrogen isotopic analysis. We applied the method to determine the amino acid contents and stable nitrogen isotopic compositions of individual amino acids from the thermally metamorphosed (above 500 °C) Antarctic carbonaceous chondrites Ivuna-like (CI)1 (or CI-like) Yamato (Y) 980115 and Ornans-like (CO)3.5 Allan Hills (ALH) A77003 with the use of gas chromatography/combustion/isotope ratio mass spectrometry. ALHA77003 was deprived of amino acids due to its extended thermal alteration history. Amino acids were unambiguously identified in Y-980115, and the δ15N values of selected amino acids (glycine +144.8 ‰; α-alanine +121.2 ‰) are clearly extraterrestrial. Y-980115 has experienced an extended period of aqueous alteration as indicated by the presence of hydrous mineral phases. It has also been exposed to at least one post-hydration short-lived thermal metamorphism. Glycine and alanine were possibly produced shortly after the accretion event of the asteroid parent body during the course of an extensive aqueous alteration event and have abstained from the short-term post-aqueous alteration heating due to the heterogeneity of the parent body composition and porosity. These carbonaceous chondrite samples are good analogs that offer important insights into the target asteroid Ryugu of the Hayabusa-2 mission, which is a C-type asteroid likely composed of heterogeneous materials including hydrated and dehydrated minerals.

  5. Isotopic composition of surface-correlated chromium in Apollo 16 lunar soils

    NASA Astrophysics Data System (ADS)

    Kitts, B. Kathleen; Podosek, Frank A.; Nichols, Robert H.; Brannon, Joyce C.; Ramezani, Jahan; Korotev, Randy L.; Jolliff, Brad L.

    2003-12-01

    We have analyzed by thermal ionization mass spectrometry (TIMS) the isotopic composition of Cr in five progressive etches of size-sorted plagioclase grains separated from lunar soils 60601 and 62281. Aliquots of the etch solutions were spiked for isotopic dilution (ID) analysis of Cr and Ca. The Ca ID data indicate that the initial etch steps represent dissolution of an average 0.1 to 0.2 μm depth from the grain surfaces, the approximate depth expected for implanted solar wind. The Cr/Ca ratio in the initial etches is several fold higher than that expected for bulk plagioclase composition, but in subsequent etches decreases to approach the bulk value. This indicates a source of Cr extrinsic to the plagioclase grains, surface-correlated and resident in the outermost fraction of a μm, which we provisionally identify as solar wind Cr. The surface-correlated Cr is isotopically anomalous and by conventional TIMS data reduction has approximately 1 permil excess 54Cr and half as great excess 53Cr. In successive etches, as the Cr/Ca ratio decreases and approaches the bulk plagioclase value, the magnitude of the apparent anomalies decreases approaching normal composition. If these results do indeed characterize the solar wind, then either the solar wind is enriched in Cr due to spallation in the solar atmosphere, or the Earth and the various parent bodies of the meteorites are isotopically distinct from the Sun and must have formed from slightly different mixes of presolar materials. Alternative interpretations include the possibility that the anomalous Cr is meteoritic rather than solar or that the observed (solar) Cr is normal except for a small admixture of spallation Cr generated on the Moon. We consider these latter possibilities less likely than the solar wind interpretation. However, they cannot be eliminated and remain working hypotheses.

  6. New perspectives on the Li isotopic composition of the upper continental crust and its weathering signature

    NASA Astrophysics Data System (ADS)

    Sauzéat, Lucie; Rudnick, Roberta L.; Chauvel, Catherine; Garçon, Marion; Tang, Ming

    2015-10-01

    Lithium isotopes are increasingly used to trace both present-day and past weathering processes at the surface of the Earth, and could potentially be used to evaluate the average degree of past weathering recorded by the upper continental crust (UCC). Yet the previous estimate of average δ7Li of the UCC has a rather large uncertainty, hindering the use of Li isotopes for this purpose. New δ7Li for desert and periglacial loess deposits (windblown dust) from several parts of the world (Europe, Argentina, China and Tajikistan) demonstrate that the former are more homogeneous than the latter, and may therefore serve as excellent proxies of the average composition of large tracts of the UCC. The Li isotopic compositions and concentrations of desert loess samples are controlled by eolian sorting that can be quantified by a binary mixing between a weathered, fine-grained end-member, dominated by phyllosilicates and having low δ7Li, and an unweathered, coarse-grained end-member, that is a mixture of quartz and plagioclase having higher δ7Li. We use correlations between insoluble elements (REE, Nd/Hf and Fe2O3/SiO2), Li concentrations (henceforth referred as [Li]), and δ7Li to estimate a new, more precise, average Li isotopic composition and concentration for the UCC: [ Li ] = 30.5 ± 3.6 (2 σ) ppm, and δ7Li = + 0.6 ± 0.6 (2 σ). The δ7Li for desert loess deposits is anti-correlated with the chemical index of alteration (CIA). Using this relationship, along with our average δ7Li, we infer that (1) the present-day CIA of the average UCC is 61-2+4 (2 σ), higher than the common reference value of 53, and (2) the average proportion of chemically weathered components is as high as 37-10+17 (2 σ)% at the surface of the Earth.

  7. An updated estimation of the stable carbon and oxygen isotopic compositions of automobile CO emissions

    NASA Astrophysics Data System (ADS)

    Tsunogai, Urumu; Hachisu, Yosuke; Komatsu, Daisuke D.; Nakagawa, Fumiko; Gamo, Toshitaka; Akiyama, Ken-ichi

    We estimate up-to-date values of the average isotopic compositions of CO emitted from automobiles. In the estimation, we determined the isotopic compositions of CO in tail pipe exhaust for four gasoline automobiles and two diesel automobiles under varying conditions of both idling and running. While the dependence on the automobile manufacturer is little, each automobile equipped with functional catalytic converter exhibits a large temporal δ13C and δ18O variation. They tend to show 13C and 18O enrichment in accordance with the reduction of CO in exhaust, suggesting that the functional catalytic converter in engines enhances the δ13C and δ18O values of CO from tail pipes through a kinetic isotope effect during CO destruction. Assuming that automobiles run a modeled driving cycle, we estimated the average δ13C and δ18O of CO to be -23.8±0.8‰ PDB and +25.3±1.0‰ SMOW, respectively, for recent gasoline automobiles, and -19.5±0.7‰ PDB and +15.1±1.0‰ SMOW, respectively, for recent diesel automobiles. While the δ13C and δ18O values of recent gasoline automobiles coincide well with the isotopic compositions of source CO in present trunk road atmosphere estimated in this study, those are +4-+6‰ ( δ13C) and +1-+3‰ ( δ18O) higher than those reported previously and also those emitted from old, non-catalyst automobiles determined in this study. Recent improvements in functional catalytic converters have enhanced and will enhance the δ13C and δ18O values of CO from automobiles.

  8. Isotopic Composition of Trapped and Cosmogenic Noble Gases in Several Martian Meteorites

    NASA Technical Reports Server (NTRS)

    Garrison, Daniel H.; Bogard, Donald D.

    1997-01-01

    Isotopic abundances of the noble gases were measured in the following Martian meteorites: two shock glass inclusions from EET79001, shock vein glass from Shergotty and Y793605, and whole rock samples of ALH84001 and QUE94201. These glass samples, when combined with literature data on a separate single glass inclusion from EET79001 and a glass vein from Zagami, permit examination of the isotopic composition of Ne, Ar, Kr, and Xe trapped from the Martian atmosphere in greater detail. The isotopic composition of Martian Ne, if actually present in these glasses, remains poorly defined. The Ar-40/Ar-36 ratio of Martian atmospheric Ar may be much less than the ratio measured by Viking and possibly as low as approx. 1900. The atmospheric Ar-36/Ar-38 ratio is less than or equal to 4.0. Martian atmospheric Kr appears to be enriched in lighter isotopes by approx. 0.4%/amu compared to both solar wind Kr and to the Martian composition previously reported. The Martian atmospheric Ar-36/Xe-132 and Kr-84/Xe-132 Xe elemental ratios are higher than those reported by Viking by factors of approx. 3.3 and approx. 2.5, respectively. Cosmogenic gases indicate space exposure ages of 13.9 +/- 1 Myr for ALH84001 and 2.7 +/- 0.6 Myr for QUE94201. Small amounts of Ne-21 produced by energetic solar protons may be present in QUE94201, but are not present in ALH84001 or Y793605. The space exposure age for Y793605 is 4.9 +/- 0.6 Myr and appears to be distinctly older than the ages for basaltic shergottites.

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